Note: Descriptions are shown in the official language in which they were submitted.
CA 02647153 2012-12-19
IMPACT RESISTANT POLYURETHANE AND POLY(UREAURETHANE) ARTICLES
AND METHODS OF MAKING THE SAME
BACKGROUND OF THE INVENTION
I. FIELD OF THE INVENTION
100011 The present invention relates to polyurethanes and poly(ureaurethanes)
prepared from branched polyols, branched polyisocyanates and/or polyisocyanate
turners, articles and coatings prepared therefrom, and methods of making the
same.
II. TECHNICAL CONSIDERATIONS
100021 A number of organic polymeric materials, for example plastics such as
polycarbonates and acrylics, have been developed as alternatives and
replacements
for glass in applications such as optical lenses, fiber optics, windows and
automotive,
nautical and aviation transparencies. For example,
in aircraft glazings both
polycarbonates, such as LEXANO, and acrylics have enjoyed widespread
acceptance.
These polymeric materials can provide advantages relative to glass, including
shatter
or penetration resistance, lighter weight for a given application,
flexibility, ease of
molding and dyeability. Unfortunately,
there are some serious disadvantages
associated with both polycarbonates and acrylics. Polycarbonates scratch
easily, and
if directly exposed to sunlight and harsh environments soon become difficult
to view
through. Acrylics, although not as scratchable as polycarbonates, do not have
the
physical properties of the polycarbonates such as heat distortion temperature
and
impact resistance. Some "high impact" strength polycarbonates can have
inconsistent
impact strength that can degrade over time, poor crack propagation resistance
(K-
factor), poor optical quality, poor solvent resistance and poor
weatherability. Even
though polycarbonates can exhibit good impact strength when impacted at low
speeds, at high impact speeds of greater than
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100031 about 1100 ft/sec (335.3 m/sec), such as those exhibited in ballistics
applications, a 9 mm bullet (125 grain) fired from about 20 feet (6.1 m) at a
speed of
about 1350 ft/sec (411 m/sec) can pass easily through a 1 inch (2.5 cm) thick
polycarbonate plastic.
[0004] Also, polycarbonates are typically extruded, which can produce optical
distortions in the extrudate in the direction of extrusion. For optical
applications such
as fighter plane canopies, polycarbonates typically must undergo an additional
processing step to remove the distortions, which can increase cost. Also, some
polycarbonates are birefringent which can also cause optical distortions. For
example,
the Abbe number of LEXAN is 34. Higher Abbe values indicate better visual
acuity
and less chromatic aberrations.
[0005] Thus, there is a need in the art to develop polymers useful for
producing
articles having good optical quality, high impact resistance, high impact
strength, high
K factor, good ballistics resistance, good solvent resistance and good
weatherability.
The ability to fabricate articles by casting or reaction injection molding
rather than
extrusion also is desirable.
SUMMARY OF THE INVENTION
[0006] Discussion of the various aspects and embodiments of polyurethanes and
poly(ureaurethanes) of the present invention have been grouped below. While
the
various aspects of the invention have been grouped for discussion purposes,
the
groupings are not intended to limit the scope of the invention and aspects of
one
grouping may be relevant to the subject matter of other groupings.
Group A
100071 In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.05 to about 0.9 equivalents of at least one branched polyol
having 4 to 12 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.1 to about 0.95 equivalents of at least one diol having 2 to 18
carbon atoms,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol and the reaction components are maintained at a temperature
of at
least about 100 C for at least about 10 minutes.
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[0008] In other non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components consisting of:
(a) about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate);
(b) about 0.3 to about 0.5 equivalents of trimethylolpropane; and
(c) about 0.3 to about 0.7 equivalents of 1,10-dodecanediol, butanediol or
pentanediol, wherein the reaction components are maintained at a temperature
of at
least about 100 C for at least about 10 minutes.
[0009] In some non-limiting embodiments, the present invention provides an
article
comprising a polyurethane comprising a reaction product of components
comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.1 to about 0.9 equivalents of at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.1 to about 0.9 equivalents of at least one diol having 2 to 12
carbon atoms,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol, and the article has a Gardner Impact strength of at least
about 200 in-
lb (23 Joules) according to ASTM-D 5420-04.
[0010] In some non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the step of reacting in a one pot process
components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.1 to about 0.9 equivalents of at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.1 to about 0.9 equivalents of at least one diol having 2 to 12
carbon atoms,
wherein the components are essentially free of polyester polyol and polyether
polyol
and the reaction components are maintained at a temperature of at least about
100 C
for at least about 10 minutes.
[0011] In other non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the steps of:
(a) reacting at least one polyisocyanate and at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form a
polyurethane prepolymer; and
(b) reacting the polyurethane prepolymer with at least one diol having 2 to
12 carbon atoms to form the polyurethane
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wherein the reaction components are maintained at a temperature of at least
about
100 C for at least about 10 minutes.
Group B
[0012] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) an isocyanate functional urethane prepolymer comprising a reaction
product of components comprising:
(i) about 1 equivalent of at least one polyisocyanate; and
(ii) about 0.1 to about 0.5 equivalents of at least one diol having 2
to 18 carbon atoms; and
(b) about 0.05 to about 0.9 equivalents of at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) up to about 0.45 equivalents of at least one diol having 2 to 18
carbon
atoms,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
Group C
[0013] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) at least one polyisocyanate selected from the group consisting of
polyisocyanate trimers and branched polyisocyanates, the
polyisocyanate having at least three isocyanate functional groups; and
(b) at least one aliphatic polyol having 4 to 18 carbon atoms and at least
two hydroxyl groups,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
[0014] In other non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components consisting of:
(a) about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate);
(b) about 1.1 equivalents of butanediol; and
(c) about 0.1 equivalents of isophorone diisocyanate trimer.
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[0015] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethane comprising the step of reacting in a one pot
process components comprising:
(a) at least one polyisocyanate trimer or branched polyisocyanate, the
polyisocyanate having at least three isocyanate functional groups; and
(b) at least one aliphatic polyol having 4 to 18 carbon atoms and at least
two hydroxyl groups,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
Group D
[0016] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) at least one polyisocyanate;
(b) at least one branched polyol having 4 to 18 carbon atoms and at least 3
hydroxyl groups; and
(c) at least one polyol having one or more bromine atoms, one or more
phosphorus atoms or combinations thereof.
[0017] In other non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components consisting of:
(a) about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate);
(b) about 0.3 to about 0.5 equivalents of trimethylolpropane;
(c) about 0.2 to about 0.5 equivalents of bis(4-(2-hydroxyethoxy)-3,5-
dibromophenyl) sulfone;
(d) about 0.2 to about 0.5 equivalents of 1,4-cyclohexane dimethanol; and
(e) about 0.2 to about 0.5 equivalents of 3,6-dithia-1,2-octanediol.
[0018] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) at least one polyisocyanate selected from the group consisting of
polyisocyanate trimers and branched polyisocyanates, the
polyisocyanate having at least three isocyanate functional groups;
(b) at least one aliphatic polyol having 4 to 18 carbon atoms and at least
2
hydroxyl groups; and
(c) at least one polyol having one or more bromine atoms, one or more
phosphorus atoms or combinations thereof.
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[0019] In some non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the step of reacting in a one pot process
components comprising:
(a) at least one polyisocyanate;
(b) at least one branched polyol having 4 to 18 carbon atoms and at least 3
hydroxyl groups; and
(c) at least one polyol having one or more bromine atoms, one or more
phosphorus atoms or combinations thereof.
[0020] In other non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the steps of:
(a) reacting at least one polyisocyanate and at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form a
polyurethane prepolymer; and
(b) reacting the polyurethane prepolymer with at least one polyol having
one or more bromine atoms, one or more phosphorus atoms or
combinations thereof to form the polyurethane.
Group E
[0021] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.3 to about 1 equivalents of at least one branched polyol having
4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.01 to about 0.3 equivalents of at least one polycarbonate diol,
wherein the reaction product components are essentially free of polyether
polyol and
amine curing agent and wherein the reaction components are maintained at a
temperature of at least about 100 C for at least about 10 minutes.
[0022] In other non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components consisting of:
(a) about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate);
(b) about 0.3 equivalents of trimethylolpropane;
(c) about 0.5 to about 0.55 equivalents of butanediol or pentanediol; and
(d) about 0.15 to about 0.2 equivalents of polyhexylene carbonate diol
wherein the reaction components are maintained at a temperature of at least
about
100 C for at least about 10 minutes.
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[0023] In some non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the step of reacting in a one pot process
components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.3 to about 1 equivalents of at least one branched polyol having
4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.01 to about 0.3 equivalents of at least one polycarbonate diol,
wherein the reaction product components are essentially free of polyether
polyol and
amine curing agent and wherein the reaction components are maintained at a
temperature of at least about 100 C for at least about 10 minutes.
[0024] In other non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the steps of:
(a) reacting at least one polyisocyanate and at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form a
polyurethane prepolymer; and
(b) reacting the polyurethane prepolymer with at least one polycarbonate
diol to form the polyurethane.
Group F
[0025] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.3 to about 1 equivalents of at least one branched polyol having
4 to 18 carbon atoms and at least 3 hydroxyl groups;
(c) about 0.01 to about 0.3 equivalents of at least one polycarbonate diol;
and
(d) about 0.1 to about 0.9 equivalents of at least one diol having 2 to 18
carbon atoms,
wherein the reaction product components are essentially free of polyether
polyol and
wherein the reaction components are maintained at a temperature of at least
about
100 C for at least about 10 minutes.
[0026] In some non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the step of reacting in a one pot process
components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
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(b) about 0.3 to about 1 equivalents of at least one branched polyol having
4 to 18 carbon atoms and at least 3 hydroxyl groups;
(c) about 0.01 to about 0.3 equivalents of at least one polycarbonate diol;
and
(d) about 0.1 to about 0.9 equivalents of at least one diol having 2 to 18
carbon atoms,
wherein the reaction product components are essentially free of polyether
polyol and
wherein the reaction components are maintained at a temperature of at least
about
100 C for at least about 10 minutes.
100271 In other non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the steps of:
(a) reacting at least one polyisocyanate and at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form a
polyurethane prepolymer; and
(b) reacting the polyurethane prepolymer with at least one polycarbonate
diol and at least one diol having 2 to 18 carbon atoms to form the
polyurethane
wherein the reaction product components are essentially free of polyether
polyol.
Group G
[0028] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.3 to about 1 equivalents of at least one branched polyol having
4 to 18 carbon atoms and at least 3 hydroxyl groups;
(c) about 0.01 to about 0.3 equivalents of at least one polyol selected
from
the group consisting of polyester polyol, polycaprolactone polyol and mixtures
thereof; and
(d) about 0.1 to about 0.7 equivalents of at least one aliphatic diol,
wherein the reaction product components are essentially free of polyether
polyol and
amine curing agent and wherein the reaction components are maintained at a
temperature of at least about 100 C for at least about 10 minutes.
[0029] In other non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components consisting of:
(a) about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate);
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(b) about 0.3 equivalents of trimethylolpropane;
(c) about 0.5 equivalents of decanediol; and
(d) about 0.2 equivalents of polycaprolactone polyol,
wherein the reaction components are maintained at a temperature of at least
about
100 C for at least about 10 minutes.
100301 In some non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the step of reacting in a one pot process
components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.3 to about 1 equivalents of at least one branched polyol having
4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.01 to about 0.3 equivalents of at least one polyol selected
from
the group consisting of polyester polyol, polycaprolactone polyol and
mixtures thereof; and
(d) about 0.1 to about 0.7 equivalents of at least one aliphatic diol,
wherein the reaction product components are essentially free of polyether
polyol and
amine curing agent.
[0031] In other non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the steps of:
(a) reacting at least one polyisocyanate and at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form a
polyurethane prepolymer; and
(b) reacting the polyurethane prepolymer with at least one polyol selected
from the group consisting of polyester polyol, polycaprolactone polyol
and mixtures thereof and about 0.1 to about 0.7 equivalents of at least
one aliphatic diol to form the polyurethane.
Group H
[0032] In some non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) a prepolymer which is the reaction product of components comprising:
(1) at least one polyisocyanate;
(2) at least one polycaprolactone polyol; and
(3) at least one polyol selected from the group consisting of
polyalkylene polyol, polyether polyol and mixtures thereof; and
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(b) at least one diol having 2 to 18 carbon atoms.
[0033] In other non-limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) a prepolymer which is the reaction product of components comprising:
(1) aliphatic or cycloaliphatic diisocyanate;
(2) polycaprolactone diol;
(3) polyethylene glycol; and
(4) polyoxyethylene and polyoxypropylene copolymer; and
(b) at least one diol having 2 to 18 carbon atoms.
[0034] In some non-limiting embodiments, the present invention provides
methods of
preparing polyurethane comprising the steps of:
(a) reacting components comprising:
1) at least one polyisocyanate;
2) at least one polycaprolactone polyol; and
3) at least one polyol selected from the group consisting of
polyalkylene polyol, polyether polyol and mixtures thereof,
to form a polyurethane prepolymer; and
(b) reacting the prepolymer with at least one diol having 2 to 18 carbon
atoms to form the polyurethane.
Group I
[0035] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s comprising a reaction product of components comprising:
(a) at least one isocyanate functional urea prepolymer comprising a
reaction product of:
(1) at least one polyisocyanate; and
(2) water; and
(b) at least one branched polyol having 4 to 18 carbon atoms and at
least 3
hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent.
[0036] In some non-limiting embodiments, the present invention provides
methods of
preparing poly(ureaurethane) comprising the steps of:
(a) reacting at least one polyisocyanate and water to form an isocyanate
functional urea prepolymer; and
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(b) reacting reaction product components comprising the isocyanate
functional urea prepolymer with at least one branched polyol having 4 to
18 carbon atoms and at least 3 hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent.
Group J
[0037] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s comprising a reaction product of components comprising:
(a) at least one isocyanate functional urea prepolymer comprising a
reaction product of:
(1) at least one polyisocyanate selected from the group consisting
of polyisocyanate trimers and branched polyisocyanates, the
polyisocyanate having at least three isocyanate functional
groups; and
(2) water; and
(b) at least one aliphatic polyol having 4 to 18 carbon atoms and at
least 2
hydroxyl groups.
[0038] In some non-limiting embodiments, the present invention provides
methods of
preparing poly(ureaurethane) comprising the steps of:
(a) reacting at least one polyisocyanate selected from the group consisting
of polyisocyanate trimers and branched polyisocyanates and water to
form an isocyanate functional urea prepolymer; and
(b) reacting reaction product components comprising the isocyanate
functional urea prepolymer with at least one aliphatic polyol having 4 to
18 carbon atoms and at least 2 hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent.
Group K
[0039] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s comprising a reaction product of components comprising:
(a) at least one isocyanate functional ureaurethane prepolymer
comprising
the reaction product of:
(1) at least one isocyanate functional urethane prepolymer
comprising the reaction product of:
(i) a first amount of at least one polyisocyanate; and
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(ii) a first amount of at least one branched polyol;
and
(2) water,
to form an isocyanate functional ureaurethane prepolymer; and
(b) a second amount of at least one polyisocyanate and a second amount
of at least one branched polyol.
[0040] In some non-limiting embodiments, the present invention provides
methods of
preparing poly(ureaurethane) comprising the steps of:
(a) reacting at least one polyisocyanate and at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups to form an
isocyanate
functional urethane prepolymer;
(b) reacting the isocyanate functional urethane prepolymer with water and
polyisocyanate to form an isocyanate functional ureaurethane prepolymer; and
(c) reacting reaction product components comprising the isocyanate
functional ureaurethane prepolymer with at least one aliphatic polyol having 4
to 18
carbon atoms and at least 2 hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent.
Group L
[0041] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s comprising a reaction product of components comprising:
(a) at least one isocyanate functional ureaurethane prepolymer
comprising
the reaction product of:
(1) at least one isocyanate functional urethane prepolymer
comprising the reaction product of:
(i) a first amount of at least one polyisocyanate selected
from the group consisting of polyisocyanate trimers and
branched polyisocyanates, the polyisocyanate having at least
three isocyanate functional groups; and
(ii) a first amount of at least one aliphatic polyol; and
(2) water,
to form an isocyanate functional ureaurethane prepolymer; and
(b) a second amount of at least one polyisocyanate and a second amount
of at least one aliphatic polyol.
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[0042] In some non-limiting embodiments, the present invention provides
methods of
preparing poly(ureaurethane) comprising the steps of:
(a) reacting at least one polyisocyanate selected from the group consisting
of polyisocyanate trimers and branched polyisocyanates and at least one
aliphatic
polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups to form an
isocyanate functional urethane prepolymer;
(b) reacting the isocyanate functional urethane prepolymer with water and
polyisocyanate to form an isocyanate functional ureaurethane prepolymer; and
(c) reacting reaction product components comprising the isocyanate
functional ureaurethane prepolymer with at least one aliphatic polyol having 4
to 18
carbon atoms and at least 2 hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent.
Group M
[0043] In other non-limiting embodiments, the present invention provides
poly(ureaurethane)s comprising a reaction product of components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.1 to about 0.9 equivalents of at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups;
(c) about 0.1 to about 0.9 equivalents of at least one aliphatic diol
having 2
to 18 carbon atoms; and
(d) at least one amine curing agent,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
[0044] In other non-limiting embodiments, the present invention provides
methods of
preparing poly(ureaurethane) comprising the step of reacting in a one pot
process
components comprising:
(a) at least one polyisocyanate;
(b) at least one branched polyol having 4 to 18 carbon atoms and at least 3
hydroxyl groups;
(c) at least one aliphatic diol having 2 to 18 carbon atoms; and
(d) amine curing agent,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
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Group N
100451 In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s comprising a reaction product of components comprising:
(a) at least one polyisocyanate selected from the group consisting of
polyisocyanate trimers and branched polyisocyanates, the
polyisocyanate having at least three isocyanate functional groups;
(b) about 0.1 to about 0.9 equivalents of at least one polyol having 4 to
18
carbon atoms and at least 2 hydroxyl groups; and
(c) at least one amine curing agent,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
100461 In some non-limiting embodiments, the present invention provides
methods of
preparing poly(ureaurethane) comprising the step of reacting in a one pot
process
components comprising:
(a) at least one polyisocyanate selected from the group consisting of
polyisocyanate trimers and branched polyisocyanates;
(b) at least one aliphatic polyol having 4 to 18 carbon atoms and at least
3
hydroxyl groups;
(c) at least one aliphatic diol having 2 to 18 carbon atoms; and
(d) amine curing agent,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol.
Group 0
100471 In some non-limiting embodiments, the present invention provides
polyurethane materials comprising a first portion of crystalline particles
having self-
orientation and bonded together to fix their orientation along a first
crystallographic
direction and a second portion of crystalline particles having self-
orientation and
bonded together to fix their orientation along a second crystallographic
direction, the
first crystallographic direction being different from the second
crystallographic
direction, wherein said crystalline particles comprise at least about 30% of
the total
volume of the polyurethane material.
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Group P
[0048] In some non-limiting embodiments, the present invention provides
methods of
preparing a polyurethane powder coating composition comprising the steps of:
reacting at least one polyisocyanate with at least one aliphatic polyol to
form a
generally solid, hydroxy functional prepolymer; melting the hydroxy functional
prepolymer; melting at least one generally solid polyisocyanate to form a
melted
polyisocyanate; mixing the hydroxy functional prepolymer and melted
polyisocyanate
to form a mixture; and solidifying the mixture to form a generally solid
powder coating
composition.
[0049] In other non-limiting embodiments, the present invention provides
methods of
preparing a polyurethane powder coating composition comprising the steps of:
reacting at least one polyisocyanate with at least one aliphatic polyol to
form a
generally solid, hydroxy functional prepolymer; dissolving the hydroxy
functional
prepolymer in a first solvent to form a first solution; dissolving at least
one generally
solid polyisocyanate in a second solvent that is the same as or compatible
with the first
solvent to form a second solution; mixing the first and second solutions; and
removing
substantially all of the solvent to form a generally solid powder coating
composition.
Group Q
[0050] In some non-limiting embodiments, the present invention provides
polyurethane compositions comprising: at least one polyurethane comprising a
reaction product of components comprising:
(a) (i) at least one polyisocyanate;
(ii) at least one branched polyol having 4 to 18 carbon atoms and at
least 3 hydroxyl groups; and
(iii) at least one diol having 2 to 18 carbon atoms; and
(b) at least one reinforcement material selected from the group consisting of
polymeric inorganic materials, nonpolymeric inorganic materials, polymeric
organic
materials, nonpolymeric organic materials, composites thereof, and
combinations
thereof.
[0051] In other non-limiting embodiments, the present invention provides
polyurethane
compositions comprising:
(a) at least one polyurethane comprising a reaction product of
components
comprising:
(i) at least one polyisocyanate;
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(ii) at least one branched polyol having 4 to 18 carbon atoms and at
least 3 hydroxyl groups; and
(iii) at least one polyol having one or more bromine atoms, one or
more phosphorus atoms or combinations thereof; and
(b) at least one reinforcement material selected from the group
consisting
of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric
organic
materials, nonpolymeric organic materials, composites thereof, and mixtures
thereof.
100521 In other non-limiting embodiments, the present invention provides
polyurethane
compositions comprising:
(a) a polyurethane comprising a reaction product of components
comprising:
(i) a prepolymer which is the reaction product of components
comprising:
(1) at least one polyisocyanate;
(2) at least one polycaprolactone polyol; and
(3) at least one polyol selected from the group consisting
of polyalkylene polyol, polyether polyol and mixtures thereof;
and
(ii) at least one diol having 2 to 18 carbon atoms; and
(b) at least one reinforcement material selected from the group
consisting
of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric
organic
materials, nonpolymeric organic materials, composites thereof, and mixtures
thereof.
[0053] In other non-limiting embodiments, the present invention provides
polyurethane
compositions comprising:
(a) at least one polyurethane comprising a reaction product of
components
comprising:
(i) at least one polyisocyanate selected from the group consisting
of polyisocyanate trimers or branched polyisocyanates, the
polyisocyanate having at least three isocyanate functional groups; and
(ii) at least one aliphatic polyol having 4 to 18 carbon atoms and at
least two hydroxyl groups; and
(b) at least one reinforcement material selected from the group
consisting
of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric
organic
materials, nonpolymeric organic materials, composites thereof, and mixtures
thereof.
- 16 -
CA 02647153 2012-12-19
100541 In other non-limiting embodiments, the present invention provides
poly(ureaurethane)s composition comprising:
(a) at least one poly(ureaurethane) comprising a reaction product of
components comprising:
(i) at least one isocyanate functional prepolymer comprising a
reaction product of:
1. at least one polyisocyanate; and
2. water; and
(ii) at least one branched polyol having 4 to 18 carbon atoms and
at
least 3 hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent;
and
(b) at least one reinforcement material selected from the group
consisting
of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric
organic
materials, nonpolymeric organic materials, composites thereof, and mixtures
thereof.
[0055] In other non-limiting embodiments, the present invention provides
poly(ureaurethane)s composition comprising:
(a) at least one poly(ureaurethane) comprising a reaction product of
components comprising:
(i) at least one isocyanate functional urethane prepolymer
comprising a reaction product of:
1. a first amount of at least one polyisocyanate; and
2. a first amount
of at least one branched polyol; and
(ii) water,
to form an isocyanate functional ureaurethane prepolymer; and
(b) a second amount of at least one polyisocyanate and a second amount
of at least one branched polyol; and
(c) at least one reinforcement material selected from the group
consisting
of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric
organic
materials, nonpolymeric organic materials, composites thereof, and mixtures
thereof.
100561 In some non-limiting embodiments, the present invention provides
methods for
forming a reinforced polyurethane composition, comprising the steps of: mixing
a
precursor solution of the reaction product components of the above
polyurethane or
poly(ureaurethane) with a precursor for the nanostructures; forming the
nanostructures
- 17 -
CA 02647153 2012-12-19
from the precursor of the nanostructures in the polyurethane matrix; and
polymerizing
the precursor of the reaction product components to form the polyurethane.
Group R
[0057] In some non-limiting embodiments, the present invention provides a
laminate
comprising:
(a) at least one layer of at least one polyurethane comprising a
reaction
product of components comprising:
(i) at least one polyisocyanate;
(ii) at least one branched polyol having 4 to 18 carbon atoms and at
least 3 hydroxyl groups; and
(iii) at least one diol having 2 to 18 carbon atoms; and
(b) at least one layer of a substrate selected from the group consisting
of
paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric
material and
combinations thereof.
[0058] In other non-limiting embodiments, the present invention provides a
laminate
comprising:
(a) at least one layer of at least one polyurethane comprising a
reaction
product of components comprising:
(i) at least one polyisocyanate;
(ii) at least one branched polyol having 4 to 18 carbon atoms and
at least 3 hydroxyl groups; and
(iii) at least one polyol having one or more bromine atoms, one or
more phosphorus atoms or combinations thereof; and
(b) at least one layer of a substrate selected from the group consisting
of
paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric
material and
combinations thereof.
[0059] In other non-limiting embodiments, the present invention provides a
laminate
comprising:
(a) at least one layer of at least one polyurethane comprising a
reaction
product of components comprising:
(i) a prepolymer which is the reaction product of components
comprising:
(1) at least one polyisocyanate;
(2) at least one polycaprolactone polyol; and
- 18 -
CA 02647153 2012-12-19
(3) at least one polyol selected from the group consisting
of polyalkylene polyol, polyether polyol and mixtures
thereof; and
(ii) at least one diol having 2 to 18 carbon atoms; and
(b) at least one layer of a substrate selected from the group consisting of
paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric
material and
combinations thereof.
100601 In other non-limiting embodiments, the present invention provides a
laminate
comprising:
(a) at least one layer of at least one polyurethane comprising a
reaction
product of components comprising:
(i) at least one polyisocyanate selected from the group consisting
of polyisocyanate trimers or branched polyisocyanates, the
polyisocyanate having at least three isocyanate functional groups; and
(ii) at least one aliphatic polyol having 4 to 18 carbon atoms and
at least two hydroxyl groups; and
(b) at least one layer of a substrate selected from the group consisting
of
paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric
material and
combinations thereof.
100611 In other non-limiting embodiments, the present invention provides a
laminate
comprising:
(a) at least one layer of at least one poly(ureaurethane) comprising a
reaction product of components comprising:
(i) at least one isocyanate functional prepolymer comprising a
reaction product of:
1. at least one polyisocyanate; and
2. water; and
(ii) at least one branched polyol having 4 to 18 carbon atoms and
at
least 3 hydroxyl groups,
wherein the reaction product components are essentially free of amine curing
agent;
and
(b) at least one layer of a substrate selected from the group consisting of
paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric
material and
combinations thereof.
- 19 -
CA 02647153 2012-12-19
[0062] In other non-limiting embodiments, the present invention provides a
laminate
comprising:
(A) at least one layer of at least one poly(ureaurethane) comprising a
reaction product of components comprising:
(a) at least one isocyanate functional ureaurethane prepolymer
comprising a reaction product of components comprising
(1) at least one isocyanate functional urethane prepolymer
comprising a reaction product of:
a. a first amount of at least one polyisocyanate; and
b. a first amount of at least one branched polyol;
and
(2) water,
to form an isocyanate functional ureaurethane prepolymer; and
(b) a second amount of at least one polyisocyanate and a second
amount of at least one branched polyol; and
(B) at least one layer of a substrate selected from the group consisting of
paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric
material and
combinations thereof.
[0063] Cured compositions, articles, laminates and methods of making and using
the
same comprising the above polyurethanes and poly(ureaurethane)s are also
provided
by the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0064] The foregoing summary, as well as the following detailed description,
will be
better understood when read in conjunction with the appended drawings. In the
drawings:
[0065] Fig. 1 is a graph of G' and G" as a function of temperature measured
using
Dynamic Mechanical Analysis (DMA) showing storage modulus, loss modulus and
tan
Delta for a casting of a polyurethane according to Example A, Formulation 1 of
the
present invention;
[0066] Fig. 2 is a graph of G' and G" as a function of temperature measured
using
Dynamic Mechanical Analysis (DMA) showing storage modulus, loss modulus and
tan
Delta for a casting of a polyurethane according to Example A, Formulation 2 of
the
present invention;
- 20 -
CA 02647153 2012-12-19
[0067] Fig. 3 is a graph of G' and G" as a function of temperature measured
using
Dynamic Mechanical Analysis (DMA) showing storage modulus, loss modulus and
tan
Delta for a casting of a polyurethane according to Example A, Formulation 40
of the
present invention;
[0068] Fig. 4 is a TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2 analyzed two weeks after formation
according
to the present invention;
[0069] Fig. 5 is a TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2 analyzed about three weeks after
formation
according to the present invention;
[0070] Fig. 6 is a TEM photomicrograph showing a first portion of a casting of
a
polyurethane according to Example A, Formulation 2 analyzed about seven months
after formation according to the present invention;
[0071] Fig. 7 is an electron diffraction pattern of a casting of the
polyurethane of
Example A, Formulation 2 of Fig. 6;
[0072] Fig. 8 is a TEM photomicrograph showing a second portion of the casting
of the
polyurethane of Fig. 6 according to Example A, Formulation 2 prepared after
aging at
ambient conditions for about seven months according to the present invention;
[0073] Fig. 9 is a TEM photomicrograph showing a first portion of a casting of
a
polyurethane according to Example A, Formulation 2 prepared after aging at
ambient
temperature for about two to four weeks;
[0074] Fig. 10 is a TEM photomicrograph showing a second portion of the
casting of
the polyurethane according to Example A, Formulation 2 shown in Fig. 9;
[0075] Fig. 11 is a TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2;
[0076] Fig. 12 is a TEM photomicrograph showing a first portion of a casting
of a
polyurethane according to Example A, Formulation 2 prepared after aging at
ambient
temperature for about seven months;
[0077] Fig. 13 is a TEM photomicrograph showing a second portion of a casting
of a
polyurethane according to Example A, Formulation 2 shown in Fig. 12;
[0078] Fig. 14 is a graph of heat flow as a function of temperature measured
using
Differential Scanning Calorimetry (DSC) for castings of a polyurethane
according to
Example A, Formulation 2 measured after aging at ambient conditions for two
weeks,
three months and seven months, respectively, according to the present
invention;
- 21 -
CA 02647153 2012-12-19
[0079] Fig. 15 is a graph of Gardner Impact as a function of Young's Modulus
for
castings of a polyurethane according to Example A, Formulations 1 and 2
measured
after aging at ambient conditions for seven months and one year, respectively,
according to the present invention;
[0080] Fig. 16 is a graph of storage modulus, loss modulus and tan delta as a
function
of temperature measured using DMA for a casting of a polyurethane prepared
according to Example A, Formulation 114, according to the present invention;
[0081] Fig. 17 is a photograph of a perspective view of a test sample of
Formulation 2,
Example A after shooting of the sample with 0.40 caliber bullets from 30 feet
(9.2 m) at
a velocity of 987 ft/sec (300.8 m/sec);
[0082] Fig. 18 is a photograph of a front elevational view of a test sample of
Formulation 2, Example A after shooting of the sample with a 12 gauge shotgun
shot
from 20 feet (6.1 m) at a velocity of 1290 ft/sec (393.2 m/sec) using heavy
game lead
shot pellets;
[0083] Fig. 19 is a photograph of a front elevational view of a test sample of
Formulation 93, Example A is a photograph of a front elevational view of a
test sample
of 9 mm bullets shot from 20 feet (6.1 m) at a velocity of 1350 ft/sec (411.5
m/sec);
[0084] Fig. 20 is a photograph of a perspective view of a test sample of
Formulation
94, Example A after shooting of the sample with a 9 mm bullet shot from 20
feet (6.1
m) at an initial velocity of 1350 ft/sec (411.5 m/sec);
[0085] Fig. 21 is a side elevational view of the sample shown in Fig. 20;
[0086] Fig. 22 is front elevational view of a portion of a composite according
to the
present invention after shooting of the sample with four 7.62 x 39 mm bullets
having a
steel core shot from an AK-47 rifle from a distance of 30 yards (27.4 m) at an
initial
velocity of 2700 ft/sec (823 m/sec);
[0087] Fig. 23 is a rear perspective view of the sample of Fig. 22.
[0088] Fig. 24 is a graph of heat flow as a function of temperature measured
using
Differential Scanning Calorimetry (DSC) for a casting of a polyurethane
prepared
according to Example A, Formulation 2 of the present invention;
[0089] Fig. 25 is a graph of heat flow as a function of temperature measured
using
(DSC) for a casting of a polyurethane prepared according to Example A,
Formulation
136 of the present invention; and
[0090] Fig. 26 is a graph of weight loss as a function of temperature measured
using
Thermogravimetric Analysis (TGA) for a casting of a polyurethane prepared
according
to Example A, Formulation 136 of the present invention.
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CA 02647153 2012-12-19
DETAILED DESCRIPTION
[0091] As used herein, spatial or directional terms, such as "inner", "left",
"right", "up",
"down", "horizontal", "vertical" and the like, relate to the invention as it
is described
herein. However, it is to be understood that the invention can assume various
alternative orientations and, accordingly, such terms are not to be considered
as
limiting. For the purposes of this specification, unless otherwise indicated,
all numbers
expressing quantities of ingredients, reaction conditions, dimensions,
physical
characteristics, and so forth used in the specification and claims are to be
understood
as being modified in all instances by the term "about." Accordingly, unless
indicated to
the contrary, the numerical parameters set forth in the following
specification and
attached claims are approximations that may vary depending upon the desired
properties sought to be obtained by the present invention. At the very least,
and not
as an attempt to limit the application of the doctrine of equivalents to the
scope of the
claims, each numerical parameter should at least be construed in light of the
number
of reported significant digits and by applying ordinary rounding techniques.
[0092] Notwithstanding that the numerical ranges and parameters setting forth
the
broad scope of the invention are approximations, the numerical values set
forth in the
specific examples are reported as precisely as possible. Any numerical value,
however, inherently contain certain errors necessarily resulting from the
standard
deviation found in their respective testing measurements.
[0093] Also, it should be understood that any numerical range recited herein
is
intended to include all sub-ranges subsumed therein. For example, a range of
"1 to
10" is intended to include any and all sub-ranges between and including the
recited
minimum value of 1 and the recited maximum value of 10, that is, all subranges
beginning with a minimum value equal to or greater than 1 and ending with a
maximum value equal to or less than 10, and all subranges in between, e.g., 1
to 6.3,
or 5.5 to 10, or 2.7 to 6.1.
[0094] "Alkyl" means an aliphatic hydrocarbon group which may be straight or
branched and comprising about 1 to about 20 carbon atoms in the chain. Non-
limiting
examples of suitable alkyl groups contain about 1 to about 18 carbon atoms in
the
chain, or about 1 to about 6 carbon atoms in the chain. Branched means that
one or
more lower alkyl groups such as methyl, ethyl or propyl, are attached to a
linear alkyl
chain. "Lower alkyl" or "short chain alkyl" means a group having about 1 to
about 6
carbon atoms in the chain which may be straight or branched. "Alkyl" may be
- 23 -
CA 02647153 2012-12-19
unsubstituted or optionally substituted by one or more substituents which may
be the
same or different, each substituent being independently selected from the
group
consisting of halo, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy,
alkylthio, amino,
-NH(alkyl), -NH(cycloalkyl), -N(alkyl)2, carboxy and ¨C(0)0-alkyl. Non-
limiting
examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl
and
t-butyl.
[0095] "Alkylene" means a difunctional group obtained by removal of a hydrogen
atom
from an alkyl group that is defined above. Non-limiting examples of alkylene
include
methylene, ethylene and propylene.
[0096] "Aryl" means an aromatic monocyclic or multicyclic ring system
comprising
about 6 to about 14 carbon atoms, or about 6 to about 10 carbon atoms. The
aryl
group can be optionally substituted with one or more "ring system
substituents" which
may be the same or different, and are as defined herein. Non-limiting examples
of
suitable aryl groups include phenyl and naphthyl.
[0097] "Heteroaryl" means an aromatic monocyclic or multicyclic ring system
comprising about 5 to about 14 ring atoms, or about 5 to about 10 ring atoms,
in which
one or more of the ring atoms is an element other than carbon, for example
nitrogen,
oxygen or sulfur, alone or in combination. In some non-limiting embodiments,
the
heteroaryls contain about 5 to about 6 ring atoms. The "heteroaryl" can be
optionally
substituted by one or more "ring system substituents" which may be the same or
different, and are as defined herein. The prefix aza, oxa or thia before the
heteroaryl
root name means that at least one of a nitrogen, oxygen or sulfur atom
respectively, is
present as a ring atom. A nitrogen atom of a heteroaryl can be optionally
oxidized to
the corresponding N-oxide. Non-limiting examples of suitable heteroaryls
include
pyridyl, pyrazinyl, furanyl, thienyl, pyrimidinyl, pyridone (including N-
substituted
pyridones), isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl,
furazanyl, pyrrolyl,
pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl,
quinoxalinyl, phthalazinyl,
oxindolyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofurazanyl,
indolyl,
azaindolyl, benzimidazolyl, benzothienyl, quinolinyl, imidazolyl,
thienopyridyl,
quinazolinyl, thienopyrimidyl,
pyrrolopyridyl, imidazopyridyl, isoquinolinyl,
benzoazaindolyl, 1,2,4-triazinyl, benzothiazolyl and the like. The term
"heteroaryl" also
refers to partially saturated heteroaryl moieties such as, for example,
tetrahydroisoquinolyl, tetrahydroquinolyl and the like.
[0098] "Aralkyl" or "arylalkyl" means an aryl-alkyl- group in which the aryl
and alkyl are
as previously described. In some non-limiting embodiments, the aralkyls
comprise a
- 24 -
CA 02647153 2012-12-19
lower alkyl group. Non-limiting examples of suitable aralkyl groups include
benzyl, 2-
phenethyl and naphthalenylmethyl. The bond to the parent moiety is through the
alkyl.
[0099] "Alkylaryl" means an alkyl-aryl- group in which the alkyl and aryl are
as
previously described. In some non-limiting embodiments, the alkylaryls
comprise a
lower alkyl group. A non-limiting example of a suitable alkylaryl group is
tolyl. The
bond to the parent moiety is through the aryl.
[00100] "Cycloalkyl" means a non-aromatic mono- or multicyclic ring system
comprising about 3 to about 10 carbon atoms, or about 5 to about 10 carbon
atoms. In
some non-limiting embodiments, the cycloalkyl ring contains about 5 to about 7
ring
atoms. The cycloalkyl can be optionally substituted with one or more "ring
system
substituents" which may be the same or different, and are as defined above.
Non-
limiting examples of suitable monocyclic cycloalkyls include cyclopropyl,
cyclopentyl,
cyclohexyl, cycloheptyl and the like. Non-limiting examples of suitable
multicyclic
cycloalkyls include 1-decalinyl, norbornyl, adamantyl and the like.
[00101] "Halogen" or "halo" means fluorine, chlorine, bromine, or iodine.
In
some non-limiting embodiments, the halogen groups are fluorine, chlorine or
bromine.
[00102] "Ring system substituent" means a substituent attached to an
aromatic
or non-aromatic ring system which, for example, replaces an available hydrogen
on
the ring system. Ring system substituents may be the same or different, each
being
independently selected from the group consisting of alkyl, alkenyl, alkynyl,
aryl,
heteroaryl, aralkyl, alkylaryl, heteroaralkyl, heteroarylalkenyl,
heteroarylalkynyl,
alkylheteroaryl, hydroxy, hydroxyalkyl, alkm, aryloxy, aralkoxy, acyl, aroyl,
halo, nitro,
cyano, carboxy, alkmcarbonyl, aryloxycarbonyl, aralkoxycarbonyl,
alkylsulfonyl,
arylsulfonyl, heteroarylsulfonyl, alkylthio, arylthio, heteroarylthio,
aralkylthio,
heteroaralkylthio, cycloalkyl, heterocyclyl, -C(=N-CN)-NH2, -C(=NH)-NH2,
NH(alkyl), Yi Y2N-, Y1Y2N-alkyl-, Y1Y2NC(0)-, Y1Y2NS02- and -SO2NY1Y2, wherein
Y1 and Y2 can be the same or different and are independently selected from the
group
consisting of hydrogen, alkyl, aryl, cycloalkyl, and aralkyl. "Ring system
substituent"
may also mean a single moiety which simultaneously replaces two available
hydrogens on two adjacent carbon atoms (one H on each carbon) on a ring
system.
Examples of such moieties are methylene dioxy, ethylenedioxy, -C(CH3)2- and
the like
which form moieties such as, for example:
=0 (0
0:1 and
- 25 -
CA 02647153 2012-12-19
[00103] "Heterocycly1"
means a non-aromatic saturated monocyclic or
multicyclic ring system comprising about 3 to about 10 ring atoms, or about 5
to about
ring atoms, in which one or more of the atoms in the ring system is an element
other than carbon, for example nitrogen, oxygen or sulfur, alone or in
combination.
There are no adjacent oxygen and/or sulfur atoms present in the ring system.
In some
non-limiting embodiments, the heterocyclyl contains about 5 to about 6 ring
atoms.
The prefix aza, oxa or thia before the heterocyclyl root name means that at
least a
nitrogen, oxygen or sulfur atom respectively is present as a ring atom. Any
¨NH in a
heterocyclyl ring may exist protected such as, for example, as an -N(Boc), -
N(CBz), -
N(Tos) group and the like; such protections are also considered part of this
invention.
The heterocyclyl can be optionally substituted by one or more "ring system
substituents" which may be the same or different, and are as defined herein.
The
nitrogen or sulfur atom of the heterocyclyl can be optionally oxidized to the
corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of
suitable
monocyclic heterocyclyl rings include piperidyl, pyrrolidinyl, piperazinyl,
morpholinyl,
thiomorpholinyl, thiazolidinyl, 1,4-dioxanyl, tetrahydrofuranyl,
tetrahydrothiophenyl,
lactam, lactone, and the like.
[00104] It should be
noted that in hetero-atom containing ring systems of this
invention, there are no hydroxyl groups on carbon atoms adjacent to a N, 0 or
S, as
well as there are no N or S groups on carbon adjacent to another heteroatom.
Thus,
for example, in the ring:
4
5
there is no -OH attached directly to carbons marked 2 and 5.
[00105] It should also
be noted that tautomeric forms such as, for example, the
moieties:
N 0
1!I and N OH
are considered equivalent in certain embodiments of this invention.
[00106]
"Heteroaralkyl" means a heteroaryl-alkyl- group in which the heteroaryl
and alkyl are as previously described. In some non-limiting embodiments, the
heteroaralkyl contains a lower alkyl group. Non-limiting
examples of suitable
- 26 -
CA 02647153 2012-12-19
heteroaralkyl groups include pyridylmethyl, and quinolin-3-ylmethyl. The bond
to the
parent moiety is through the alkyl.
[00107] "Hydroxyalkyl"
means a HO-alkyl- group in which alkyl is as previously
defined. In some non-limiting embodiments, the hydroxyalkyl contains a lower
alkyl
group. Non-limiting examples of suitable hydroxyalkyl groups include
hydroxymethyl
and 2-hydroxyethyl.
[00108] "Alkoxy" means
an alkyl-0- group in which the alkyl group is as
previously described. Non-limiting
examples of suitable alkoxy groups include
methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. The bond to the parent
moiety
is through the ether oxygen.
[00109] "Aryloxy"
means an aryl-0- group in which the aryl group is as
previously described. Non-limiting examples of suitable aryloxy groups include
phenoxy and naphthoxy. The bond to the parent moiety is through the ether
oxygen.
[00110] "Alkylthio"
means an alkyl-S- group in which the alkyl group is as
previously described. Non-limiting examples of suitable alkylthio groups
include
methylthio and ethylthio. The bond to the parent moiety is through the sulfur.
[00111] "Arylthio"
means an aryl-S- group in which the aryl group is as
previously described. Non-limiting examples of suitable arylthio groups
include
phenylthio and naphthylthio. The bond to the parent moiety is through the
sulfur.
[00112] "Aralkylthio"
means an aralkyl-S- group in which the aralkyl group is as
previously described. Non-limiting
example of a suitable aralkylthio group is
benzylthio. The bond to the parent moiety is through the sulfur.
[00113]
"Alkoxycarbonyl" means an alkyl-O-00- group. Non-limiting examples
of suitable alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.
The
bond to the parent moiety is through the carbonyl.
[00114]
"Aryloxycarbonyl" means an aryl-O-C(0)- group. Non-limiting examples
of suitable aryloxycarbonyl groups include phenoxycarbonyl and
naphthoxycarbonyl.
The bond to the parent moiety is through the carbonyl.
[00115]
"Aralkoxycarbonyl" means an aralkyl-O-C(0)- group. A non-limiting
example of a suitable aralkoxycarbonyl group is benzyloxycarbonyl. The bond to
the
parent moiety is through the carbonyl.
[00116]
"Alkylsulfonyl" means an alkyl-S(02)- group. In some non-limiting
embodiments, the alkylsulfonyl group includes a lower alkyl group. The bond to
the
parent moiety is through the sulfonyl.
- 27 -
CA 02647153 2012-12-19
[00117] "Arylsulfonyl" means an aryl-S(02)- group. The bond to the parent
moiety is through the sulfonyl.
[00118] The term "substituted" means that one or more hydrogens on the
designated atom is replaced with a selection from the indicated group,
provided that
the designated atom's normal valency under the existing circumstances is not
exceeded, and that the substitution results in a stable compound. Combinations
of
substituents and/or variables are permissible only if such combinations result
in stable
compounds.
[00119] The term "optionally substituted" means optional substitution with
the
specified groups, radicals or moieties.
[00120] It should also be noted that any carbon as well as heteroatom with
unsatisfied valences in the text, schemes, examples and Tables herein is
assumed to
have the sufficient number of hydrogen atom(s) to satisfy the valences.
[00121] When a functional group in a compound is termed "protected", this
means that the group is in modified form to preclude undesired side reactions
at the
protected site when the compound is subjected to a reaction. Suitable
protecting
groups will be recognized by those with ordinary skill in the art as well as
by reference
to standard textbooks such as, for example, T. W. Greene et al, Protective
Groups in
organic Synthesis (1991), Wiley, New York.
[00122] When any variable (e.g., aryl, heterocycle, R2, etc.) occurs more
than
one time in any constituent, its definition on each occurrence is independent
of its
definition at every other occurrence.
[00123] As used herein, the term "composition" is intended to encompass a
product comprising the specified ingredients in the specified amounts, as well
as any
product which results, directly or indirectly, from combination of the
specified
ingredients in the specified amounts.
[00124] As used herein, "formed from" or "prepared from" denotes open,
e.g.,
"comprising," claim language. As such, it is intended that a composition
"formed from"
or "prepared from" a list of recited components be a composition comprising at
least
these recited components or the reaction product of at least these recited
components,
and can further comprise other, non-recited components, during the
composition's
formation or preparation. As used herein, the phrase "reaction product of
means
chemical reaction product(s) of the recited components, and can include
partial
reaction products as well as fully reacted products.
- 28 -
CA 02647153 2012-12-19
[00125] As used
herein, the term "polymer" in meant to encompass oligomers,
and includes without limitation both homopolymers and copolymers. The term
"prepolymer" means a compound, monomer or oligomer used to prepare a polymer,
and includes without limitation both homopolymer and copolymer oligomers.
[00126] The phrase
"thermoplastic polymer" means a polymer that undergoes
liquid flow upon heating and can be soluble in solvents.
[00127] The phrase
"thermoset polymer" means a polymer that solidifies or
"sets" irreversibly upon curing or crosslinking. Once cured, a crosslinked
thermoset
polymer will not melt upon the application of heat and is generally insoluble
in solvents.
[00128] As used
herein, the term "cure" as used in connection with a
composition, e.g., "composition when cured" or a "cured composition", shall
mean that
any curable or crosslinkable components of the composition are at least
partially cured
or crosslinked. In some non-limiting embodiments of the present invention, the
crosslink density of the crosslinkable components, i.e., the degree of
crosslinking,
ranges from about 5% to about 100% of complete crosslinking. In other non-
limiting
embodiments, the crosslink density ranges from about 35% to about 85% of full
crosslinking. In other non-limiting embodiments, the crosslink density ranges
from
about 50% to about 85% of full crosslinking. One skilled in the art will
understand that
the presence and degree of crosslinking, i.e., the crosslink density, can be
determined
by a variety of methods, such as dynamic mechanical thermal analysis (DMA)
using a
TA Instruments DMA 2980 DMA analyzer over a temperature range of -65 F (-18 C)
to
350 F (177 C) conducted under nitrogen according to ASTM D 4065-01. This
method
determines the glass transition temperature and crosslink density of free
films of
coatings or polymers. These physical properties of a cured material are
related to the
structure of the crosslinked network. In an embodiment of the present
invention, the
sufficiency of cure is evaluated relative to the solvent resistance of a cured
film of the
polymer. For example, solvent resistance can be measured by determining the
number of double acetone rubs. For purposes of the present invention, a
coating is
deemed to be "cured" when the film can withstand a minimum of 100 double
acetone
rubs without substantial softening of the film and no removal of the film.
[00129] Curing of a
polymerizable composition can be obtained by subjecting
the composition to curing conditions, such as but not limited to thermal
curing,
irradiation, etc., leading to the reaction of reactive groups of the
composition and
resulting in polymerization and formation of a solid polymerizate. When a
polymerizable composition is subjected to curing conditions, following
polymerization
- 29 -
CA 02647153 2012-12-19
and after reaction of most of the reactive groups occurs, the rate of reaction
of the
remaining unreacted reactive groups becomes progressively slower. In some non-
limiting embodiments, the polymerizable composition can be subjected to curing
conditions until it is at least partially cured. The term "at least partially
cured" means
subjecting the polymerizable composition to curing conditions, wherein
reaction of at
least a portion of the reactive groups of the composition occurs, to form a
solid
polymerizate. The at least partially cured polymerizate can be demolded and,
for
example, used to prepare articles such as windows, cut into test pieces or
subjected to
machining operations, such as optical lens processing. In some non-limiting
embodiments, the polymerizable composition can be subjected to curing
conditions
such that a substantially complete cure is attained and wherein further
exposure to
curing conditions results in no significant further improvement in polymer
properties,
such as strength or hardness.
[00130] The term "polyurethane" is intended to include not only
polyurethanes
that are formed from the reaction of polyisocyanates and polyols but also
poly(ureaurethane)(s) that are prepared from the reaction of polyisocyanates
with
polyols and water and/or polyamines.
[00131] The polyurethanes and poly(ureaurethane)s of the present invention
can be useful in applications in which one or more of the following properties
are
desired: transparency, high optical quality, high Abbe number, low color,
energy-
absorption, stiffness, moisture stability, ultraviolet light stability,
weathering resistance,
low water absorption, hydrolytic stability and bullet or explosive resistance.
[00132] In some embodiments, cured articles prepared from the polyurethanes
and poly(ureaurethane)s of the present invention are generally clear, can have
a
luminous transmittance of at least about 80 percent, less than about 2 percent
haze
and show no visual change after 1,000 hours of light and water exposure
according to
ASTM D-1499-64.
[00133] Polyurethanes and poly(ureaurethane)s of the present invention can
be
formed into articles having a variety of shapes and dimensions, such as flat
sheets or
curved shapes. Non-limiting examples of useful methods for forming articles
include
heat treatment, pressure casting, or pouring liquid polyurethane or
poly(ureaurethane)
into a mold and curing the product to form a molded article.
[00134] Generally, the polyurethanes and poly(ureaurethane)s of the present
invention comprise a reaction product of components comprising at least one
polyisocyanate and at least one aliphatic polyol having 4 to 18 carbon atoms
and at
- 30 -
CA 02647153 2012-12-19
least 2 or at least 3 hydroxyl groups, wherein at least one of the
polyisocyanate(s)
and/or the aliphatic polyol(s) is branched.
[00135] In the present
invention, at least one of the isocyanate and/or at least
one of the polyols is branched. As used herein, "branched" means a chain of
atoms
with one or more side chains attached to it. Branching occurs by the
replacement of a
substituent, e.g, a hydrogen atom, with a covalently bonded substituent or
moiety, e.g,
an alkyl group. While not intending to be bound by any theory, it is believed
that
branching of the polyisocyanate and/or polyol can increase the free volume
within the
polymer matrix, thereby providing room for the molecules to move. The
molecules can
orient and rotate into configurations and alignments having favorable energy
states
which can provide good impact properties and/or high modulus of elasticity for
the
cured polymer matrix. As shown in Figs. 1, 2 and 3, Dynamic Mechanical
Analysis
(DMA) of polyurethane castings prepared according to Examples 1, 2 and 40,
respectively, for loss modulus as a function of temperature show a low
temperature
transition at about -70 C. DMA analysis was conducted over a temperature range
of -
65 F (-18 C) to 350 F (177 C) under nitrogen according to ASTM D 4065-01.
While
not intending to be bound by any theory, it is believed that this low
temperature
transition is due to molecular torsional mobility at that temperature and is
believed to
contribute to the high impact strength of these polymers.
[00136] When a
viscoelastic material is subjected to an oscillatory vibration,
some energy is stored in the polymer, which is proportional to the elastic
component of
the modulus G', or storage modulus, and some of the energy is converted to
heat
through internal friction, or viscous dissipation of the energy, which is
termed the loss
modulus G". The maximum in the loss modulus is termed tan delta, which is the
maximum in internal friction, damping, or viscous energy dissipation.
[00137] High light
transmittance, glassy polymers rarely exhibit high impact
strength. Polycarbonate
plastics such as LEXAN0 can exhibit a similar low
temperature transition, but can have lower impact strength and lower Young's
modulus.
[00138] The physical
properties of the polyurethanes and poly(ureaurethane)s
of the present invention are derived from their molecular structure and are
determined
by the selection of building blocks, e.g., the selection of the reactants, the
ratio of the
hard crystalline and soft amorphous segments, and the supra-molecular
structures
caused by atomic interactions between chains.
- 31 -
CA 02647153 2012-12-19
[00139] Hard segments,
i.e., the crystalline or semi-crystalline region of the
urethane polymer, result from the reaction of the isocyanate and a chain
extender,
such as an aliphatic polyol having 4 to 18 carbon atoms or low molecular
weight polyol
having a molecular weight of less than about 200 discussed herein. Generally,
the soft
segment, i.e., the amorphous, rubbery region of the urethane polymer, results
from the
reaction of the isocyanate and a polymer backbone component, for example a
polyester polyol (such as a polycarbonate polyol) or a polyether polyol or
short chain
diols that have not formed crystalline regions.
[00140] The
qualitative contribution of a particular organic polyol to either the
hard or soft segment when mixed and reacted with other polyurethane-forming
components can be readily determined by measuring the Fischer microhardness of
the
resulting cured polyurethane according to ISO 14577-1:2002.
[00141] In some non-
limiting embodiments, the hard segment content of the
polyurethane ranges from about 10 to about 100 weight percent, or about 50 to
about
100 weight percent, or about 70 to about 100 weight percent. The hard segment
content is the percentage by weight of the hard segment linkages present in
the
polymer and can be calculated by determining the total number of equivalents,
and
from this the total weight of all reactants, and dividing the total weight of
the hard
segment linkages obtainable from these reactants by the total weight of the
reactants
themselves. The following example will further explain the calculation. In
Example I,
Formulation 1 which follows, a polyurethane article according to the invention
was
prepared by reacting 0.7 equivalents of 1,4-butanediol, 0.3 equivalents of
trimethylolpropane and one equivalent of 4,4'-methylene-bis-(cyclohexyl
isocyanate)
(DESMODURTm W). The equivalent weight of the 1,4-butanediol is 45 g/eq., the
equivalent weight of the trimethylolpropane is 44.7 g/eq. (corrected for
impurities) and
the equivalent weight of the DESMODURTm W is 131.2 g/eq. Therefore, the actual
weight of ingredients used is 31.54 parts by weight of 1,4-butanediol, 13.2
parts by
weight of trimethylolpropane and 131.2 parts by weight of DESMODURTm W or a
total
reactant weight of 175. parts by weight. One equivalent of 1,4-butanediol will
yield one
equivalent of hard segment linkage, where the hard segment linkage is 1,4-
butanediol/DESMODURTm W dimer. The equivalent
weight of a 1,4-
butanediol/DESMODURTm W dimer linkage is 176 g/eq. so that the total weight of
the
hard segment linkages determined by multiplying the equivalent weight of the
hard
segment dimer by the number of equivalents of 1,4-butanediol would be 123.2
g/eq.
Thus, the total weight of the 1,4-butanediol/DESMODURTm W dimer linkage,
123.2,
- 32 -
CA 02647153 2012-12-19
divided by the total weight of the reactants, 175.7, multiplied by 100 to
convert to
percentages would give a percentage by weight of hard segment linkage of 70
percent
by weight.
[00142] Both PlexiglasTM and stretched acrylic absorb quite a bit of water
from
the atmosphere. In accelerated tests such as QUV-B or soaking in water at room
temperature, surprisingly, polyurethanes according to the present invention
including
short chain diols such as butanediol and pentanediol, absorbed essentially no
water in
water vapor transmission rate studies and after soaking in water for about 24
hours.
While not intending to be bound by any theory, it is believed that even though
these
plastics are very polar, the hydrogen bonding in the hard segment domains is
strong
enough to block water vapor transmission and uptake of water. In comparison,
stretched acrylic will absorb enough water to cause severe swelling of the
plastic, to
the point that it cracks in-plane, like layers of onion skin separating until
it falls apart.
The low water absorption can also mitigate any hydrolysis degradation of the
urethane
groups in the polymer.
[00143] Discussion of the various aspects and embodiments of polyurethanes
and poly(ureaurethanes) of the present invention have been grouped generally
in
groups A - Q below. As stated above, these groupings are not intended to limit
the
scope of the invention and aspects of one grouping may be relevant to the
subject
matter of other groupings. Also, limitations as to amounts of reactants in one
grouping
are not necessarily intended to limit amounts of the same component in other
groupings, although appropriate amounts may be the same for a different
grouping
unless otherwise indicated.
- 33 -
CA 02647153 2012-12-19
Group A
[00144] In some non-
limiting embodiments, the present invention provides
polyurethanes comprising a reaction product of components comprising:
(a) about 1 equivalent of at least one polyisocyanate;
(b) about 0.05 to about 0.9 equivalents of at least one branched polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and
(c) about 0.1 to about 0.95 equivalents of at least one diol having 2 to 18
carbon atoms,
wherein the reaction product components are essentially free of polyester
polyol and
polyether polyol and wherein the reaction components are maintained at a
temperature of at least about 100 C for at least about 10 minutes.
[00145] As used
herein, the term "equivalent" means the mass in grams of a
substance which will react with one mole (6.022 x 1023 electrons) of another
substance. As used herein, "equivalent weight" is effectively equal to the
amount of a
substance in moles, divided by the valence or number of functional reactive
groups of
the substance.
[00146] As used
herein, the term "isocyanate" includes compounds, monomers,
oligomers and polymers comprising at least one or at least two ¨N=C=0
functional
groups and/or at least one or at least two ¨N=C=S (isothiocyanate) groups.
Monofunctional isocyanates can be used as chain terminators or to provide
terminal
groups during polymerization. As used herein, "polyisocyanate" means an
isocyanate
comprising at least two ¨N=C=O functional groups and/or at least two
¨N=C=S (isothiocyanate) groups, such as diisocyanates or triisocyanates, as
well as
dimers and trimers or biurets of the isocyanates discussed herein. Suitable
isocyanates are capable of forming a covalent bond with a reactive group such
as
hydroxyl, thiol or amine functional group. Isocyanates useful in the present
invention
can be branched or unbranched. As discussed above, use of branched isocyanates
may be desirable to increase the free volume within the polymer matrix to
provide
space for the molecules to move.
[00147] Isocyanates
useful in the present invention include "modified",
"unmodified" and mixtures of "modified" and "unmodified" isocyanates. The
isocyanates can have "free", "blocked" or partially blocked isocyanate groups.
The
term "modified" means that the aforementioned isocyanates are changed in a
known
manner to introduce biuret, urea, carbodiimide, urethane or isocyanurate
groups or
blocking groups. In some non-limiting embodiments, the "modified" isocyanate
is
- 34 -
CA 02647153 2012-12-19
obtained by cycloaddition processes to yield dimers and timers of the
isocyanate, i.e.,
polyisocyanates. Free isocyanate groups are extremely reactive. In order to
control
the reactivity of isocyanate group-containing components, the NCO groups may
be
blocked with certain selected organic compounds that render the isocyanate
group
inert to reactive hydrogen compounds at room temperature. When heated to
elevated
temperatures, e.g., ranging from about 90 C to about 200 C, the blocked
isocyanates
release the blocking agent and react in the same way as the original unblocked
or free
isocyanate.
[00148] Generally,
compounds used to block isocyanates are organic
compounds that have active hydrogen atoms, e.g., volatile alcohols, epsilon-
caprolactam or ketoxime compounds. Non-limiting
examples of suitable blocking
compounds include phenol, cresol, nonylphenol, epsilon-caprolactam and methyl
ethyl
ketoxime.
[00149] As used
herein, the NCO in the NCO:OH ratio represents the free
isocyanate of free isocyanate-containing materials, and of blocked or
partially blocked
isocyanate-containing materials after the release of the blocking agent. In
some
cases, it is not possible to remove all of the blocking agent. In those
situations, more
of the blocked isocyanate-containing material would be used to attain the
desired level
of free NCO.
[00150] The molecular
weight of the isocyanate and isothiocyanate can vary
widely. In alternate non-limiting embodiments, the number average molecular
weight
(Mn) of each can be at least about 100 grams/mole, or at least about 150
grams/mole,
or less than about 15,000 grams/mole, or less than about 5,000 grams/mole. The
number average molecular weight can be determined using known methods, such as
by gel permeation chromatography (GPC) using polystyrene standards.
[00151] Non-limiting
examples of suitable isocyanates include aliphatic,
cycloaliphatic, aromatic and heterocyclic isocyanates, dimers and trimers
thereof and
mixtures thereof. Useful cycloaliphatic isocyanates include those in which one
or more
of the isocyanato groups are attached directly to the cycloaliphatic ring and
cycloaliphatic isocyanates in which one or more of the isocyanato groups are
not
attached directly to the cycloaliphatic ring. Useful aromatic isocyanates
include those
in which one or more of the isocyanato groups are attached directly to the
aromatic
ring, and aromatic isocyanates in which one or more of the isocyanato groups
are not
attached directly to the aromatic ring. Useful heterocyclic isocyanates
include those in
which one or more of the isocyanato groups are attached directly to the
heterocyclic
- 35 -
CA 02647153 2012-12-19
ring and heterocyclic isocyanates in which one or more of the isocyanato
groups are
not attached directly to the heterocyclic ring.
[00152] Cycloaliphatic
diisocyanates are desirable for use in the present
invention because they are not adversely affected by ultraviolet light and can
yield
polyurethanes having high impact energy absorption levels, which make them
desirable for glass replacements and bilayer safety glass applications.
Also,
polyurethanes prepared with cycloaliphatic diisocyanates are not adversely
affected by
conventional processing temperatures. When an aromatic polyisocyanate is used,
generally care should be taken to select a material that does not cause the
polyurethane to color (e.g., yellow).
[00153] In some non-
limiting embodiments, the aliphatic and cycloaliphatic
diisocyanates can comprise about 6 to about 100 carbon atoms linked in a
straight
chain or cyclized and having two isocyanate reactive end groups.
[00154] Non-limiting
examples of suitable aliphatic isocyanates include straight
chain isocyanates such as ethylene diisocyanate, trimethylene diisocyanate,
1,6-
hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, hexamethylene
diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate,
decamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene
triisocyanate, bis(isocyanatoethyl)-carbonate, bis(isocyanatoethyl)ether.
[00155] Other non-
limiting examples of suitable aliphatic isocyanates include
branched isocyanates such as trimethylhexane diisocyanate,
trimethylhexamethylene
diisocyanate (TMDI), 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane
diisocyanate, 2,4,4,-trimethylhexamethylene diisocyanate, 1,8-diisocyanato-4-
(isocyanatomethyl)octane, 2,5,7-trimethy1-1,8-diisocyanato-5-
(isocyanatomethyl)
octane, 2-isocyanatopropy1-2,6-diisocyanatohexanoate, lysinediisocyanate
methyl
ester and lysinetriisocyanate methyl ester.
[00156] Non-limiting
examples of suitable cycloaliphatic isocyanates include
dinuclear compounds bridged by an isopropylidene group or an alkylene group of
1 to
3 carbon atoms. Non-limiting examples of suitable cycloaliphatic isocyanates
include
1 ,l'-methylene-bis-(4-isocyanatocyclohexane) or 4,4'-
methylene-bis-(cyclohexyl
isocyanate) (such as DESMODURTm W commercially available from Bayer Corp. of
Pittsburgh, Pennsylvania), 4,4'-isopropylidene-bis-(cyclohexyl isocyanate),
1,4-
cyclohexyl diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate, 3-
isocyanato
methyl-3,5,5-trimethylcyclohexyl isocyanate (a branched isocyanate also known
as
isophorone diisocyanate or IPDI) which is commercially available from Arco
Chemical
- 36 -
CA 02647153 2012-12-19
Co. of Newtown Square, Pennsylvania and meta-tetramethylxylylene diisocyanate
(a
branched isocyanate also known as 1,3-bis(1-isocyanato-1-methylethyft-benzene
which is commercially available from Cytec Industries Inc. of West Patterson,
New
Jersey under the tradename TMXD16 (Meta) Aliphatic lsocyanate) and mixtures
thereof.
[00157] Other useful din uclear cycloaliphatic diisocyanates include those
formed through an alkylene group of from 1 to 3 carbon atoms inclusive, and
which
can be substituted with nitro, chlorine, alkyl, alkoxy and other groups that
are not
reactive with hydroxyl groups (or active hydrogens) providing they are not
positioned
so as to render the isocyanate group unreactive. Also, hydrogenated aromatic
diisocyanates such as hydrogenated toluene diisocyanate may be used. Dinuclear
diisocyanates in which one of the rings is saturated and the other
unsaturated, which
are prepared by partially hydrogenating aromatic diisocyanates such as
diphenyl
methane diisocyanates, diphenyl isopropylidene diisocyanate and diphenylene
diisocyanate, may also be used.
[00158] Mixtures of cycloaliphatic diisocyanates with aliphatic
diisocyanates
and/or aromatic diisocyanates may also be used. An example is 4,4'-methylene-
bis-
(cyclohexyl isocyanate) with commercial isomer mixtures of toluene
diisocyanate or
meta-ph enylene diisocyanate.
[00159] Thioisocyanates corresponding to the above diisocyanates can be
used, as well as mixed compounds containing both an isocyanate and a
thioisocyanate group.
[00160] Non-limiting examples of suitable isocyanates can include but are
not
limited to DESMODURTm W, DESMODURTm N 3300 (hexamethylene diisocyanate
trimer), DESMODURTm N 3400 (60% hexamethylene diisocyanate dimer and 40%
hexamethylene diisocyanate trimer), which are commercially available from
Bayer
Corp.
[00161] In some non-limiting embodiments, the isocyanate can include 1,1'-
methylene-bis-(4-isocyanatocyclohexane) (also known as 4,4'-methylene-bis-
(cyclohexyl isocyanate)) and isomeric mixtures thereof. As used herein, the
term
"isomeric mixtures" refers to a mixture of the cis-cis, trans-trans, and cis-
trans isomers
of the isocyanate. Non-limiting examples of isomeric mixtures suitable for use
in the
present invention can include the trans-trans isomer of 4,4'-
methylenebis(cyclohexyl
isocyanate), hereinafter referred to as "PICM" (paraisocyanato
cyclohexylmethane),
the cis-trans isomer of PICM, the cis-cis isomer of PICM, and mixtures
thereof. Three
- 37 -
CA 02647153 2012-12-19
suitable isomers of 4,4'-methylenebis(cyclohexyl isocyanate) (also known as
1,1'-
methylenebis(4-isocyanatocyclohexane) for use in the present invention are
shown
below.
/t..-cii
OCN H CO
trans, trans
NCO
cis, trans
cis, cis
1001621 In some non-limiting embodiments, the PICM used in this invention
can
be prepared by phosgenating the 4,4'-methylenebis(cyclohexyl amine) (PACM) by
procedures well known in the art such as the procedures disclosed in U.S.
Patent Nos.
2,644,007 and 2,680,127. The PACM isomer mixtures, upon phosgenation, can
produce PICM in a liquid phase, a partially liquid phase, or a solid phase at
room
temperature. The PACM isomer mixtures can be obtained by the hydrogenation of
methylenedianiline and/or by fractional crystallization of PACM isomer
mixtures in the
presence of water and alcohols such as methanol and ethanol.
[00163] In some non-limiting embodiments, the isomeric mixture can comprise
from about 10 to about 100 weight percent of the trans, trans isomer of 4,4'-
methylenebis(cyclohexyl isocyanate)(PICM), or about 30 to about 100 weight
percent,
or about 50 to about 100 weight percent, or about 75 to about 100 weight
percent. In
other non-limiting embodiments, the cycloaliphatic isocyanate can consist
essentially
of the trans, trans isomer of 1,1'-methylene-bis-(4-isocyanatocyclohexane)
(also
known as 4,4'-methylene-bis-(cyclohexyl isocyanate)), e.g., at least about 80
weight
percent of the trans, trans isomer of 1,1'-methylene-bis-(4-
isocyanatocyclohexane), or
at least about 90 weight percent of the trans, trans isomer of 1,1'-methylene-
bis-(4-
isocyanatocyclohexane), or at least about 95 weight percent of the trans,
trans isomer
- 38 -
CA 02647153 2012-12-19
of 1,1'-methylene-bis-(4-isocyanatocyclohexane) and in other non-limiting
embodiments consists of about 100 weight percent of the trans, trans isomer of
1,1'-
methylene-bis-(4-isocyanatocyclohexane).
[00164] Non-limiting
examples of suitable polyisocyanates for use in the present
invention include polyisocyanates and polyisothiocyanates having backbone
linkages
such as urethane linkages (-NH-C(0)-0-), thiourethane linkages (-NH-C(0)-S-),
thiocarbamate linkages (-NH-C(S)-0-), dithiourethane linkages (-NH-C(S)-S-),
polyamide linkages, and combinations thereof.
[00165] Other non-
limiting examples of suitable polyisocyanates include
ethylen ically unsaturated polyisocyanates and polyisothiocyanates; a licycl
ic
polyisocyanates and polyisothiocyanates; aromatic polyisocyanates and
polyisothiocyanates wherein the isocyanate groups are not bonded directly to
the
aromatic ring, e.g., oc,ce-xylylene diisocyanate; aromatic polyisocyanates and
polyisothiocyanates wherein the isocyanate groups are bonded directly to the
aromatic
ring, e.g., benzene diisocyanate; aliphatic polyisocyanates and
polyisothiocyanates
containing sulfide linkages; aromatic polyisocyanates and polyisothiocyanates
containing sulfide or disulfide linkages; aromatic polyisocyanates and
polyisothiocyanates containing sulfone linkages; sulfonic ester-type
polyisocyanates
and polyisothiocyanates, e.g., 4-methy1-3-isocyanatobenzenesulfony1-4'-
isocyanato-
phenol ester; aromatic sulfonic amide-type polyisocyanates and
polyisothiocyanates;
sulfur-containing heterocyclic polyisocyanates and polyisothiocyanates, e.g.,
thiophene-2,5-diisocyanate; halogenated, alkylated, alkoxylated, nitrated,
carbodiimide
modified, urea modified and biuret modified derivatives of isocyanates; and
dimerized
and trimerized products of isocyanates.
[00166] Non-limiting
examples of suitable ethylenically unsaturated
polyisocyanates include butene diisocyanate and 1,3-butadiene-1,4-
diisocyanate.
Non-limiting examples of suitable alicyclic polyisocyanates include isophorone
diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate,
bis(isocyanatomethyl) cyclohexane,
bis(isocyanatocyclohexyl)methane,
bis(isocyanatocyclohexyl)-2,2-propane,
bis(isocyanatocyclohexyl)-1,2-ethane, 2-
isocyanatomethy1-3-(3-isocyanatopropy1)-5-isocyanatomethyl-bicyclo[2.2.1]-
heptane,
2- isocyan atomethy1-3-(3-isocyan atopropy1)-6-isocya natomethyl-
bicyclo[2.2.1]-heptane,
2- isocyanatomethy1-2-(3-isocyan atopropy1)-5-isocya natomethyl-bicyclo[2.2.11-
heptan e,
2-isocyanatomethy1-2-(3-isocyanatopropy1)-6-isocyanatomethyl-bicyclo[2.2.1]-
heptane,
2-isocyanatomethy1-3-(3-isocyanatopropy1)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-
- 39 -
CA 02647153 2012-12-19
heptane, 2-
isocyanatomethy1-2-(3-isocyanatopropy1)-5-(2-isocyanatoethyl)-
bicyclo[2.2.1]-heptane and 2-
isocyanatomethy1-2-(3-isocyanatopropy1)-6-(2-
isocyanatoethyl)-bicyclo[2.2.1]-heptane.
[00167] Non-limiting
examples of suitable aromatic polyisocyanates wherein the
isocyanate groups are not bonded directly to the aromatic ring include a,a'-
xylene
diisocyanate, bis(isocyanatoethyl)benzene, OC,a,ced-tetramethylxylene
diisocyanate,
1 ,3-bis(1-isocyanato-1-methylethyl)benzene,
bis(isocyanatobutyl)benzene,
bis(isocyanatomethyl)naphthalene,
bis(isocyanatomethyl)diphenyl ether,
bis(isocyanatoethyl) phthalate, mesitylene triisocyanate and
2,5-
d i(isocya natomethyl)furan.
[00168] Non-limiting
examples of suitable aromatic polyisocyanates having
isocyanate groups bonded directly to the aromatic ring include phenylene
diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate,
dimethylphenylene diisocyanate, diethylphenylene diisocyanate,
diisopropylphenylene
diisocyanate, trimethylbenzene triisocyanate, benzene diisocyanate, benzene
triisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate,
biphenyl
diisocyanate, ortho- toluidine diisocyanate, ortho-tolylidine diisocyanate,
ortho-tolylene
diisocyanate, 4,4'-diphenylmethane diisocyanate, bis(3-methy1-4-
isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxy-
bipheny1-
4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric 4,4'-
diphenylmethane
diisocyanate, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate,
4-
methyldiphenylmethane-3,5,2',4',6'-pentaisocyanate, diphenylether
diisocyanate,
bis(isocya natophenyleth er)ethyleneg lyco I,
bis(isocyanatophenylether)-1,3-
propyleneglycol, benzophenone diisocyanate, carbazole diisocyanate,
ethylcarbazole
diisocyanate and dichlorocarbazole diisocyanate.
[00169] In some non-
limiting embodiments, sulfur-containing isocyanates of the
following general formula (I) can be used:
SVR1 NCO
( I ) OCNN
'Rio
wherein R10 and R11 are each independently C1 to C3 alkyl.
1001701 Non-limiting
examples of suitable aliphatic polyisocyanates containing
sulfide linkages include thiodiethyl diisocyanate, thiodipropyl diisocyanate,
dithiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithiodimethyl
diisocyanate,
- 40 -
CA 02647153 2012-12-19
dithiodiethyl diisocyanate, dithiodipropyl diisocyanate and
dicyclohexylsulfide-4,4'-
diisocyanate. Non-limiting examples of aromatic polyisocyanates containing
sulfide or
disulfide linkages include but are not limited to diphenylsulfide-2,4'-
diisocyanate,
diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzyl
thioether,
bis(4-isocyanatomethylbenzene)-sulfide, diphenyldisulfide-4,4'-diisocyanate,
2,2'-
dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-
dimethyldiphenyldisulfide-5,5'-
diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4,4'-
d imethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-
dimethoxydiphenyldisulfide-4,4'-
diisocyanate and 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate.
[00171] Non-limiting
examples of suitable aromatic polyisocyanates containing
sulfone linkages include diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-
3,3'-
diisocyanate, benzidinesulfone-4,4'-diisocyanate,
diphenylmethanesulfone-4,4'-
diisocyanate, 4-methyld iphenylmethanesulfo ne-2,4'-d iisocyan ate, 4,4'-
dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-
4,4'-
diisocyanatodibenzylsulfone, 4,4'-dimethyldiphenylsulfone-3,3'-diisocyanate,
4,4'-di-
tert-butyl-diphenylsulfone-3,3'-diisocyanate and 4,4'-dichlorodiphenylsulfone-
3,3'-
d iisocya nate.
[00172] Non-limiting
examples of aromatic sulfonic amide-type polyisocyanates
include 4-methy1-3-
isocyanato-benzene-sulfonylanilide-3'-methy1-4'-isocyanate,
dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-
methoxybenzenesulfonyl-
ethylenediamine-3,3'-diisocyanate and 4-methy1-3-isocyanato-benzene-
sulfonylanilide-
4-ethy1-3'-isocyanate.
[00173] Non-limiting
examples of suitable isothiocyanates include cyclohexane
diisothiocyanates; aromatic isothiocyanates wherein the isothiocyanate
group(s) are
not bonded directly to the aromatic ring; aromatic isothiocyanates wherein the
isothiocyanate group(s) are bonded directly to the aromatic ring; heterocyclic
isothiocyanates; carbonyl polyisothiocyanates; aliphatic polyisothiocyanates
containing
sulfide linkages; and mixtures thereof.
[00174] Other non-
limiting examples of suitable isothiocyanates include
aromatic polyisothiocyanates wherein the isothiocyanate groups are bonded
directly to
the aromatic ring, such as phenylene diisothiocyanate; heterocyclic
polyisothiocyanates, such as 2,4,6-triisothicyanato-1,3,5-triazine and
thiophene-2,5-
diisothiocyanate; carbonyl polyisothiocyanates; aliphatic polyisothiocyanates
containing sulfide linkages, such as thiobis(3-isothiocyanatopropane);
aromatic
polyisothiocyanates containing sulfur atoms in addition to those of the
isothiocyanate
- 41 -
CA 02647153 2012-12-19
groups; halogenated, alkylated, alkoxylated, nitrated, carbodiimide modified,
urea
modified and biuret modified derivatives of these polyisothiocyanates; and
dimerized
and trimerized products of these isothiocyanates.
1001751 Non-limiting
examples of suitable aliphatic polyisothiocyanates include
1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-
diisothiocyanatobutane
and 1,6-diisothiocyanatohexane. Non-limiting
examples of aromatic
polyisothiocyanates having isothiocyanate groups bonded directly to the
aromatic ring
include 1,2-diisothiocyanatobenzene, 1,3-
diisothiocyanatobenzene, 1,4-
diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-
xylene,
4,4'-diisothiocyanato-1,1'-biphenyl, 1,1'-methylenebis(4-
isothiocyanatobenzene), 1,1'-
methylenebis(4-isoth iocyanato-2-methylbenzene), 1 ,l'-methylenebis(4-isoth
iocyanato-
3-methylbenzene), 1 ,1'- (1,2-ethane-diy1)bis(4-isothiocyanatobenzene),
4,4'-
diisothiocyanatobenzophenenone, 4,4'-diisothiocyanato-3,3'-
dimethylbenzophenone,
benzanilide-3,4'-diisothiocyanate, diphenylether-
4,4'-diisothiocyanate and
diphenylamine-4,4'-diisothiocyanate.
1001761 Non-limiting
examples of suitable carbonyl isothiocyanates include
hexane-dioyl diisothiocyanate, nonanedioyl
diisothiocyanate, carbonic
diisothiocyanate, 1,3-benzenedicarbonyl diisothiocyanate, 1,4-
benzenedicarbonyl
diisothiocyanate and (2,2'-bipyridine)-4,4'-dicarbonyl diisothiocyanate.
Non-limiting
examples of suitable aromatic polyisothiocyanates containing sulfur atoms in
addition
to those of the isothiocyanate groups, include 1-isothiocyanato-4-[(2-
isothiocyanato)sulfonyl]benzene, thiobis(4-
isoth iocyanatobenzene), sulfonylbis(4-
isothiocyanatobenzene), sulfinylbis(4-isothiocyanatobenzene),
dithiobis(4-
isoth iocyanatobenzene), 4-
isothiocyanato-1-[(4-isothiocyanatopheny1)-sulfonyl]-2-
methoxybenzene, 4-methyl-3-isothicyanatobenzene-sulfony1-4'-isothiocyanate
phenyl
ester and 4-methy1-3-
isothiocyanatobenzene-sulfonylanilide-3'-methy1-4'-
isoth iocya nate.
[00177] Other non-
limiting examples of isocyanates having isocyanate and
isothiocyanate groups include materials having aliphatic, alicyclic, aromatic
or
heterocyclic groups and which optionally can contain sulfur atoms in addition
to those
of the isothiocyanate groups. Non-limiting examples of such materials include
1-
isocyanato-3-isoth iocyanato propa ne, 1- isocyan ato-
5-isothiocyanatopentane, 1-
isocyanato-6-isothiocyanatohexane, isocyanatocarbonyl isothiocyanate, 1-
isocyanato-
4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methy1-3-
isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4,6-diisothiocyanato-1,3,5-
triazine,
- 42 -
CA 02647153 2012-12-19
4-isocyanato-4'-isothiocyanato-diphenyl sulfide and 2-
isocyanato-2'-
isoth iocyanatodiethyl disulfide.
[00178] In some non-
limiting embodiments, the isocyanate comprises at least
one triisocyanate or at least one polyisocyanate trimer. Non-limiting examples
of such
isocyanates include aromatic triisocyanates such as tris(4-iso-
cyanatophenyl)methane
(DESMODURTm R), 1,3,5-tris(3-isocyanato-4-methylphenyI)-2,3,6-trioxohexahydro-
1,3,5 triazine (DESMODURTm IL); adducts of aromatic diisocyanates such as the
adduct of 2,4-tolylene diisocyanate (TDI, 2,4-diisocyanatotoluene) and
trimethylolpropane (DESMODURTm L); and from aliphatic triisocyanates such as N-
isocyanatohexylaminocarbonyl-N,N'-bis(isocyanatohexyl)urea (DESMODURTm N),
2 ,4 ,6-trioxo-1 ,3,5-tris(6-isocyanatohexyl) hexa hyd ro-1,3,5-triazine
(DESMODURTm
N3390), 2,4,6-trioxo-
1,3,5-tris(5-isocyanato-1,3,3-trimethylcyclo-
hexylmethyl)hexahydro-1,3,5-triazine (DESMODURTm Z4370), and
4-
(isocyanatomethyl)-1,8-octane diisocyanate. The above DESMODURTm products are
commercially available from Bayer Corp. Also useful are the biuret of
hexanediisocyanate, polymeric methane diisocyanate, and polymeric isophorone
diisocyanate. Trimers of hexamethylene diisocyanate, isophorone diisocyanate
and
tetramethylxylylene diisocyanate
[00179] In some non-
limiting embodiments, the polyisocyanate used to make a
polyurethane polyol prepolymer as a precursor is a cycloaliphatic compound,
such as
a dinuclear compound bridged by an isopropylidene group or an alkylene group
of 1 to
3 carbon atoms.
[00180] The reaction
components for preparing the polyurethane of Group A
also comprise about 0.1 to about 0.9 equivalents of at least one branched
polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups. As discussed
above, the
branched polyol may increase the free volume within the polymer matrix to
provide
space for the molecules to move or rotate when impacted.
[00181] As used
herein, the term "polyol" includes compounds, monomers,
oligomers and polymers comprising at least two hydroxyl groups (such as diols)
or at
least three hydroxyl groups (such as triols), higher functional polyols and
mixtures
thereof. Suitable polyols are capable of forming a covalent bond with a
reactive group
such as an isocyanate functional group.
[00182] Non-limiting
examples of suitable polyols include aliphatic,
cycloaliphatic, aromatic, heterocyclic, oligomeric, and polymeric polyols and
mixtures
- 43 -
CA 02647153 2012-12-19
thereof. In some embodiments, such as for transparencies or windows exposed to
sunlight, aliphatic or cycloaliphatic polyols can be used.
[00183] The number of carbon atoms in the polyol described above for Group
A
can range from 4 to 18, or from 4 to 12, or from 4 to 10, or from 4 to 8, or
from 4 to 6
carbon atoms. In some non-limiting embodiments, one or more carbon atoms in
the
polyol can be replaced with one or more heteroatoms, such as N, S, or 0.
[00184] As discussed above, the branched polyol useful as a reaction
product
for preparing the polyurethane of Group A has 4 to 18 carbon atoms and at
least 3
hydroxyl groups. Non-limiting examples of trifunctional, tetrafunctional or
higher
polyols suitable for use as the branched polyol include branched chain alkane
polyols
such as glycerol or glycerin, tetramethylolmethane, trimethylolethane (for
example
1,1 ,1-trimethylolethane), trimethylolpropane (TMP) (for
example
1,1,1-trimethylolpropane), erythritol, pentaerythritol, dipentaerythritol,
tripentaerythritol,
sorbitan, alkoxylated derivatives thereof (discussed below) and mixtures
thereof.
[00185] In some non-limiting embodiments, the polyol can be a cycloalkane
polyol, such as trimethylene bis(1,3,5-cyclohexanetriol).
[00186] In some non-limiting embodiments, the polyol can be an aromatic
polyol, such as trimethylene bis(1,3,5-benzenetriol).
[00187] Further non-limiting examples of suitable polyols include the
aforementioned polyols which can be alkoxylated derivatives, such as
ethoxylated,
propoxylated and butoxylated. In alternate non-limiting embodiments, the
following
polyols can be alkoxylated with from 1 to 10 alkoxy groups: glycerol,
trimethylolethane,
trimethylolpropane, benzenetriol, cyclohexanetriol, erythritol,
pentaerythritol, sorbitol,
mannitol, sorbitan, dipentaerythritol and tripentaerythritol. In alternate non-
limiting
embodiments, alkoxylated, ethoxylated and propoxylated polyols and mixtures
thereof
can be used alone or in combination with unalkoxylated, unethoxylated and
unpropoxylated polyols having at least three hydroxyl groups and mixtures
thereof.
The number of alkoxy groups can be from 1 to 10, or from 2 to 8 or any
rational
number between 1 and 10. In a non-limiting embodiment, the alkoxy group can be
ethoxy and the number of ethoxy groups can be 1 to 5 units. In another non-
limiting
embodiment, the polyol can be trimethylolpropane having up to 2 ethoxy groups.
Non-
limiting examples of suitable alkoxylated polyols include ethoxylated
trimethylolpropane, propoxylated trimethylolpropane, ethoxylated
trimethylolethane,
and mixtures thereof.
[00188] Mixtures of any of the above polyols can be used.
- 44 -
CA 02647153 2012-12-19
1001891 In some embodiments, the polyurethanes of the present invention can
be thermoplastics, for example those polyurethanes having a molecular weight
per
crosslink of at least about 6000 g/mole.
[00190] In some non-limiting embodiments, the branched polyol having 4 to
18
carbon atoms can have a number average molecular weight of about 100 to about
500
grams/mole. In some non-limiting embodiments, the polyol can have a number
average molecular weight of less than about 450 grams/mole. In other non-
limiting
embodiments, the polyol can have a number average molecular weight of less
than
about 200 grams/mole.
1001911 The reaction components for preparing the polyurethane of Group A
also comprise about 0.1 to about 0.9 equivalents of at least one diol having 2
to 18
carbon atoms, or from about 2 to about 14 carbon atoms, or from 2 to 10 carbon
atoms, or from 2 to 6 carbon atoms. In some non-limiting embodiments, one or
more
carbon atoms in the diol can be replaced with one or more heteroatoms, such as
N, S,
or O.
[00192] Non-limiting examples of suitable diols include straight chain
alkane
diols such as ethylene glycol, diethylene glycol, triethylene glycol,
tetraethylene glycol,
1,2-ethanediol, propane diols such as 1,2-propanediol and 1,3-propanediol,
butane
diols such as 1,2- butanediol, 1,3- butanediol, and 1,4-butanediol, pentane
diols such
as 1,5-pentanediol, 1,3-pentanediol and 2,4-pentanediol, hexane diols such as
1,6-
hexanediol and 2,5-hexanediol, heptane diols such as 2,4-heptanediol, octane
diols
such as 1,8-octanediol, nonane diols such as 1,9-nonanediol, decane diols such
as
1,10-decanediol, dodecane diols such as 1,12-dodecanediol, octadecanediols
such as
1,18-octadecanediol, sorbitol, mannitol, and mixtures thereof. In some non-
limiting
embodiments, the diol is a propane diol such as 1,2-propanediol and 1,3-
propanediol,
or butane diol such as 1,2- butanediol, 1,3- butanediol, and 1,4-butanediol.
In some
non-limiting embodiments, one or more carbon atoms in the polyol can be
replaced
with one or more heteroatoms, such as N, S, or 0, for example sulfonated
polyols,
such as dithio-octane bis diol, thiodiethanol such as 2,2-thiodiethanol, or
3,6-dithia-1,2-
octanediol.
[00193] Other non-limiting examples of suitable diols include those
represented
by the following formula:
H., õ.=
0 R R"\ 0-- I-1
(I)
- 45 -
CA 02647153 2012-12-19
wherein R represents Co to C18 divalent linear or branched aliphatic,
cycloaliphatic,
aromatic, heterocyclic, or oligomeric saturated alkylene radical or mixtures
thereof; C2
to C18 divalent organic radical containing at least one element selected from
the group
consisting of sulfur, oxygen and silicon in addition to carbon and hydrogen
atoms; C5
to C18 divalent saturated cycloalkylene radical; or C5 to C18 divalent
saturated
heterocycloalkylene radical; and R' and R" can be present or absent and, if
present,
each independently represent C1 to C18 divalent linear or branched aliphatic,
cycloaliphatic, aromatic, heterocyclic, polymeric, or oligomeric saturated
alkylene
radical or mixtures thereof.
1001941 Other non-
limiting examples of suitable diols include branched chain
alkane diols, such as propylene glycol, dipropylene glycol, tripropylene
glycol,
neopentyl glycol, 2-methyl-butanediol. 2,2,4-trimethy1-1,3-pentanediol, 2-
methy1-1,3-
pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2 ,2-dimethy1-
1,3-
propanediol, dibutyl 1,3-propanediol, polyalkylene glycols such as
polyethylene
glycols, and mixtures thereof.
1001951 In some non-
limiting embodiments, the diol can be a cycloalkane diol,
such as cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanols (CHDM),
such as 1,4-cyclohexanedimethanol, cyclododecanediol, 4,4'-isopropylidene-
biscyclohexanol, hydroxypropylcyclohexanol,
cyclohexanediethanol, 1,2-
bis(hydroxymethyl)-
cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 4,4'-isopropylidene-
biscyclohexanol,
bis(4-hydroxycyclohexanol)methane and mixtures thereof.
1001961 In some non-
limiting embodiments, the diol can be an aromatic diol,
such as dihydroxybenzene, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl
alcohol and dihydroxytoluene; bisphenols, such as, 4,4'-
isopropylidenediphenol, 4,4'-
oxybisphenol, 4,4'-dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein,
bis(4-
hydroxyphenyl)methane, 4,4'-(1,2-ethenediy1)bisphenol and 4,4'-
sulfonylbisphenol;
halogenated bisphenols, such as 4,4'-isopropylidenebis(2,6-dibromophenol),
4,4'-
isopropylidenebis(2,6-dichlorophenol) and 4,4'-
isopropylidenebis(2,3,5,6-
tetrachlorophenol); alkoxylated bisphenols, which can have, for example,
ethoxy,
propoxy, a-butoxy and I3-butoxy groups; and biscyclohexanols, which can be
prepared
by hydrogenating the corresponding bisphenols, such as 4,4'-isopropylidene-
biscyclohexanol, 4,4'-oxybiscyclohexanol, 4,4'-thiobiscyclohexanol and bis(4-
hydroxycyclohexanol)methane, the alkoxylation product of 1 mole of 2,2-bis(4-
hydroxyphenyl)propane (i.e., bisphenol-A) and 2 moles of propylene oxide,
- 46 -
CA 02647153 2012-12-19
hydroxyalkyl terephthalates such as meta or para bis(2-hydroxyethyl)
terephthalate,
bis(hydroxyethyl) hydroquinone and mixtures thereof.
[00197] In some non-limiting embodiments, the diol can be an heterocyclic
diol,
for example a dihydroxy piperidine such as 1,4-bis(hydroxyethyl)piperazine.
[00198] In some non-limiting embodiments, the diol can be a diol of an
amide or
alkane amide (such as ethanediamide (oxamide)), for example N,N',bis(2-
hyd roxyethyl)oxamide
[00199] In some non-limiting embodiments, the diol can be a diol of a
propionate, such as 2,2-dimethy1-3-hydroxpropy1-2,2-dimethyl-3-
hydroxypropionate.
[00200] In some non-limiting embodiments, the diol can be a diol of a
hydantoin,
such as bishydroxypropyl hydantoin.
[00201] In some non-limiting embodiments, the diol can be a diol of a
phthalate,
such as meta or para bis(2-hydroxyethyl) terephthalate.
[00202] In some non-limiting embodiments, the diol can be a diol of a
hydroquinone, such as a dihydroxyethylhydroquinone.
[00203] In some non-limiting embodiments, the diol can be a diol of an
isocyanurate, such as dihydroxyethyl isocyanurate.
[00204] In some non-limiting embodiments, the diol for use in the present
invention can be an SH-containing material, such as polythiols having at least
three
thiol groups and 4 to 18 carbon atoms. Non-limiting examples of suitable
polythiols
can include but are not limited to aliphatic polythiols, cycloaliphatic
polythiols, aromatic
polythiols, heterocyclic polythiols, polymeric polythiols, oligomeric
polythiols and
mixtures thereof. The sulfur-containing active hydrogen-containing material
can have
linkages including but not limited to ether linkages (-0-), sulfide linkages (-
S-),
polysulfide linkages (-Sr-, wherein x is at least 2, or from 2 to 4) and
combinations of
such linkages. As used herein, the terms "thiol," "thiol group," "mercapto" or
"mercapto group" refer to an -SH group which is capable of forming a
thiourethane
linkage, (i.e., -NH-C(0)-S-) with an isocyanate group or a dithioruethane
linkage (i.e., -
NH-C(S)-S-) with an isothiocyanate group.
[00205] In some non-limiting embodiments, the components of the
polyurethane
are essentially free of SH-containing materials, i.e., comprise less than
about 5 weight
percent of SH-containing materials, in other non-limiting embodiments comprise
less
than about 2 weight percent of SH-containing materials, and in other non-
limiting
embodiments are free of SH-containing materials.
- 47 -
CA 02647153 2012-12-19
[00206] In some non-limiting embodiments, the diol having 4 to 18 carbon
atoms can have a number average molecular weight of about 200 to about 10,000
grams/mole, or less than about 500 grams/mole, or less than about 200
grams/mole.
[00207] Mixtures of any of the above diols can be used.
[00208] In some non-limiting embodiments, the reaction components for
preparing the polyurethane of Group A can further comprise one or more non-
branched triols and/or one or more non-branched higher functional polyols.
[00209] Non-limiting examples of suitable non-branched triols and non-
branched higher functional polyols include aliphatic, cycloaliphatic,
aromatic,
heterocyclic, oligomeric, and polymeric polyols and mixtures thereof.
[00210] In some non-limiting embodiments, the polyol can be a cycloalkane
polyol, such as cyclohexanetriol (for example 1,3,5-cyclohexanetriol).
[00211] In some non-limiting embodiments, the polyol can be an aromatic
polyol, such as benzenetriol (for example 1,2,3-benzenetriol, 1,2,4-
benzenetriol, and
1,3 ,5-benzenetriol) and phenolphthalein.
[00212] In some non-limiting embodiments, the polyol can be a polyol of an
isocyanurate, such as tris hydroxyethyl isocyanurate.
[00213] In some non-limiting embodiments, the reaction components for
preparing the polyurethane of Group A can further comprise one or more
branched or
unbranched polyols (diols, triols, and/or higher functional polyols) having
more than 18
carbon atoms.
[00214] Non-limiting examples of suitable polyols having more than 18
carbon
atoms include straight or branched chain aliphatic polyols, cycloaliphatic
polyols,
cycloaliphatic polyols, aromatic polyols, heterocyclic polyols, oligomeric
polyols,
polymeric polyols and mixtures thereof.
[00215] Non-limiting examples of suitable straight or branched chain
aliphatic
polyols having more than 18 carbon atoms include 1,18-icosanediol and 1,24-
tetracosanediol.
[00216] Other non-limiting examples of suitable polyols having more than 18
carbon atoms include those represented by the following formula:
R'
0 R' R"\ H (II)
[00217] wherein R represents CO to C30 divalent linear or branched
aliphatic,
cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkylene
radical or
mixtures thereof; C2 to C30 divalent organic radical containing at least one
element
- 48 -
CA 02647153 2012-12-19
selected from the group consisting of sulfur, oxygen and silicon in addition
to carbon
and hydrogen atoms; C5 to C30 divalent saturated cycloalkylene radical; or C5
to C30
divalent saturated heterocycloalkylene radical; and R' and R" can be present
or absent
and, if present, each independently represent C1 to C30 divalent linear or
branched
aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric, or oligomeric
saturated
alkylene radical or mixtures thereof.
[00218] Non-limiting examples of suitable cycloaliphatic polyols having
more
than 18 carbon atoms include biscyclohexanols having more than 18 carbon
atoms,
which can be prepared by hydrogenating the corresponding bisphenols.
[00219] Non-limiting examples of suitable aromatic polyols having more than
18
carbon atoms include bisphenols, alkoxylated bisphenols, such as alkoxylated
4,4'-
isopropylidenediphenol which can have from 3 to 70 alkoxy groups, and
[00220] Other non-limiting examples of suitable oligomeric or polymeric
polyols
having more than 18 carbon atoms include higher polyalkylene glycols such as
polyethylene glycols having number average molecular weights ranging from
about
200 grams/mole to about 2,000 grams/mole, and mixtures thereof.
[00221] In some non-limiting embodiments, the polyol for use in the present
invention can be an SH-containing material, such as polythiols having at least
two thiol
groups or at least three thiol groups and at least 18 carbon atoms. Non-
limiting
examples of suitable polythiols can include but are not limited to aliphatic
polythiols,
cycloaliphatic polythiols, aromatic polythiols, heterocyclic polythiols,
polymeric
polythiols, oligomeric polythiols and mixtures thereof. The sulfur-containing
active
hydrogen-containing material can have linkages including but not limited to
ether
linkages (-0-), sulfide linkages (-S-), polysulfide linkages (-Sr-, wherein x
is at least 2,
or from 2 to 4) and combinations of such linkages. As used herein, the terms
"thiol,"
"thiol group," "mercapto" or "mercapto group" refer to an ¨SH group which is
capable
of forming a thiourethane linkage, (i.e., -NH-C(0)-S-) with an isocyanate
group or a
dithioruethane linkage (i.e., -NH-C(S)-S-) with an isothiocyanate group.
[00222] In some non-limiting embodiments, the components of the
polyurethane
are essentially free of SH-containing materials, e.g., contain less than about
5 weight
percent of SH-containing materials, in other non-limiting embodiments contain
less
than about 2 weight percent of SH-containing materials, and in other non-
limiting
embodiments are free of SH-containing materials.
[00223] In some non-limiting embodiments, the polyol having at least 18
carbon
atoms can have a number average molecular weight of about 200 to about 5,000
- 49 -
CA 02647153 2012-12-19
grams/mole, or about 200 to about 4,000 grams/mole, or at least about 200
grams/mole, or at least about 400 grams/mole, or at least about 1000
grams/mole, or
at least about 2000 grams/mole. In some non-limiting embodiments, the polyol
can
have a number average molecular weight of less than about 5,000 grams/mole, or
less
than about 4,000 grams/mole, or less than about 3,000 grams/mole, or less than
about
2,000 grams/mole, or less than about 1,000 grams/mole, or less than about 500
grams/mole.
[00224] Mixtures of any of the above polyols can be used. For example, the
polyol can comprise trimethylolpropane and the diol can comprise butanecliol
and/or
pentanediol.
[00225] As discussed above, the amount of branched polyol used to form the
polyurethane of Group A is about 0.1 to about 0.9 equivalents. In some non-
limiting
embodiments, the amount of branched polyol used to form the polyurethane is
about
0.3 to about 0.9 equivalents. In other non-limiting embodiments, the amount of
branched polyol used to form the polyurethane is about 0.3 equivalents.
[00226] As discussed above, the amount of diol used to form the
polyurethane
of Group A is about 0.1 to about 0.9 equivalents. In some non-limiting
embodiments,
the amount of diol used to form the polyurethane is about 0.3 to about 0.9
equivalents.
In other non-limiting embodiments, the amount of diol used to form the
polyurethane is
about 0.3 equivalents.
[00227] In some non-limiting embodiments of the polyurethane of Group A,
the
reaction components comprise about 0.1 to about 0.9 equivalents of at least
one
branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups and
about
0.1 to about 0.9 equivalents of at least one diol having 2 to 18 carbon atoms,
per 1
equivalent of at least one polyisocyanate, wherein the reaction product
components
are essentially free of polyester polyol and polyether polyol and wherein the
reaction
components are maintained at a temperature of at least about 100 C for at
least about
minutes.
[00228] In some non-limiting embodiments, the polyurethane comprises a
reaction product of components consisting of: about 1 equivalent of 4,4'-
methylene-
bis-(cyclohexyl isocyanate); about 0.3 to about 0.5 equivalents of
trimethylolpropane;
and about 0.3 to about 0.7 equivalents of butanediol or pentanediol, or about
0.7
equivalents of butanediol or pentanediol, wherein the reaction components are
maintained at a temperature of at least about 100 C for at least about 10
minutes.
- 50 -
CA 02647153 2012-12-19
[00229] In another embodiment, the present invention provides polyurethanes
of
Group A comprising a reaction product of components consisting of: about 1
equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3
equivalents of
trimethylolpropane; and about 0.7 equivalents of 1,10-dodecanediol, wherein
the
reaction components are maintained at a temperature of at least about 100 C
for at
least about 10 minutes.
[00230] In another embodiment, the present invention provides polyurethanes
of
Group A comprising a reaction product of components consisting of: about 1
equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3
equivalents of
trimethylolpropane; and about 0.7 equivalents of 1,5-pentanediol, wherein the
reaction
components are maintained at a temperature of at least about 100 C for at
least about
minutes.
[00231] In another embodiment, the present invention provides polyurethanes
of
Group A comprising a reaction product of components consisting of: about 1
equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3
equivalents of
trimethylolpropane; about 0.7 equivalents of 1,4-butanediol, wherein the
reaction
components are maintained at a temperature of at least about 100 C for at
least about
10 minutes.
[00232] In another embodiment, the present invention provides polyurethanes
of
Group A comprising a reaction product of components consisting of: about 1
equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.4
equivalents of
trimethylolpropane; about 0.6 equivalents of 1,18-octadecanediol, wherein the
reaction
components are maintained at a temperature of at least about 100 C for at
least about
10 minutes.
[00233] The polyurethanes of Group A can exhibit good ballistics
resistance,
e.g., resistance to perforation, penetration or cracking due to impact from a
projectile
such as bullet or shot which is shot from a handgun, shotgun, rifle, AK-47, or
other
shooting device or explosives. In some embodiments, the polyurethanes of Group
A
of 0.75" (1.9 cm) thickness or greater will stop or deflect: a 9 mm, 125 grain
bullet shot
at an initial velocity of 1350 ft/sec (411.5 m/sec) from 20 feet; a 0.40
caliber bullet shot
at an initial velocity of 987ft/sec (300.8 m/sec) bullet from 20 feet (6.1 m);
and/or a 12
gauge shotgun shot at an initial velocity of 1290 ft/sec (393.2 m/sec) from 20
feet (6.1
m).
Group B
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CA 02647153 2012-12-19
[00234] In some non-limiting embodiments, the present invention provides
polyurethanes of Group B comprising a reaction product of components
comprising:
(a) an isocyanate functional urethane prepolymer comprising a reaction product
of
components comprising: (i) about 1 equivalent of at least one polyisocyanate;
and (ii)
about 0.1 to about 0.5 equivalents of at least one diol having 2 to 18 carbon
atoms;
and (b) about 0.05 to about 0.9 equivalents of at least one polyol having 4 to
18 carbon
atoms and at least 3 hydroxyl groups; and (c) up to about 0.45 equivalents of
at least
one diol having 2 to 18 carbon atoms, wherein the reaction product components
are
essentially free of polyester polyol and polyether polyol.
[00235] Non-limiting examples and amounts of suitable polyisocyanates,
diols
and polyols for use as reaction products for preparing the polyurethanes of
Group B
are discussed in detail above with respect to Group A. Methods for preparing
polyurethanes of Group B are discussed in detail below.
Group C
[00236] In some non-limiting embodiments, the present invention provides
polyurethanes of Group C comprising a reaction product of components
comprising: at
least one polyisocyanate selected from the group consisting of polyisocyanate
trimers
and branched polyisocyanates, the polyisocyanate having at least three
isocyanate
functional groups; and at least one aliphatic polyol having 4 to 18 carbon
atoms and at
least two hydroxyl groups, wherein the reaction product components are
essentially
free of polyester polyol and polyether polyol.
[00237] In other non-limiting embodiments, the present invention provides
polyurethanes of Group C comprising a reaction product of components
consisting of:
about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 1.1
equivalents of butanediol; and about 0.1 equivalents of isophorone
diisocyanate timer.
[00238] Non-limiting examples of suitable polyisocyanate trimers, branched
polyisocyanates and aliphatic polyols (including but not limited to straight
chain,
branched or cycloaliphatic polyols) for use in as reaction products for
preparing the
polyurethanes of Group C are discussed in detail above with respect to Group
A.
Similar amounts of polyisocyanate trimer(s) and/or branched polyisocyanate(s)
can be
used as described for the polyisocyanate of Group A above. Also, mixtures of
polyisocyanate trimer(s) and/or branched polyisocyanate(s) with other non-
branched
and non-trimer polyisocyanates described above can be used to form the
polyurethanes of Group C.
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CA 02647153 2012-12-19
1002391 In some non-limiting embodiments of the polyurethane of Group C,
the
reaction components comprise about 0.1 to about 0.9 equivalents of at least
one
branched polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups per
1
equivalent of at least one polyisocyanate, and in other non-limiting
embodiments about
0.3 to about 0.9 equivalents of at least one aliphatic polyol having 2 to 18
carbon
atoms, wherein the reaction product components are essentially free of
polyester
polyol and polyether polyol.
1002401 As discussed above, in some non-limiting embodiments of Group A,
Group B and Group C, the reaction product components are essentially free of
polyester polyol and polyether polyol. As used herein, "essentially free of
polyester
polyol and polyether polyol" means that the reaction product components
comprise
less than about 10 weight percent of polyester polyol and/or polyether polyol,
or less
than about 5 weight percent of polyester polyol and/or polyether polyol, or
less than
about 2 weight percent of polyester polyol and/or polyether polyol or is free
of
polyester polyol and/or polyether polyol.
1002411 Non-limiting examples of such polyester polyols include polyester
glycols, polycaprolactone polyols, polycarbonate polyols and mixtures thereof.
Polyester glycols can include the esterification products of one or more
dicarboxylic
acids having from four to ten carbon atoms, such as but not limited to adipic,
succinic
or sebacic acids, with one or more low molecular weight glycols having from
two to ten
carbon atoms, such as but not limited to ethylene glycol, propylene glycol,
diethylene
glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and 1,10-decanediol.
Esterification procedures for producing polyester polyols are described, for
example, in
the article D.M. Young, F. Hostettler et al., "Polyesters from Lactone," Union
Carbide
F-40, p. 147.
1002421 Non-limiting examples of polycaprolactone polyols include those
prepared by condensing caprolactone in the presence of difunctional active
hydrogen
material such as water or low molecular weight glycols, for example ethylene
glycol
and propylene glycol. Non-limiting examples of suitable polycaprolactone
polyols can
include commercially available materials designated as the CAPATM series from
Solvay Chemical of Houston, Texas such as CAPATM 2047A and CAPATM 2077A, and
the TONETm series from Dow Chemical of Midland, Michigan such as TONETm 0201,
0210, 0230 & 0241. In some non-limiting embodiments, the polycaprolactone
polyol
has a molecular weight ranging from about 500 to about 2000 grams per mole, or
about 500 to about 1000 grams per mole.
- 53 -
CA 02647153 2012-12-19
[00243] Non-limiting examples of polycarbonate polyols include aliphatic
polycarbonate diols, for example those based upon alkylene glycols, ether
glycols,
alicyclic glycols or mixtures thereof. In some embodiments, the alkylene
groups for
preparing the polycarbonate polyol can comprise from 5 to 10 carbon atoms and
can
be straight chain, cycloalkylene or combinations thereof. Non-limiting
examples of
such alkylene groups include hexylene, octylene, decylene, cyclohexylene and
cyclohexyldimethylene. Suitable polycarbonate polyols can be prepared, in non-
limiting examples, by reacting a hydroxy terminated alkylene glycol with a
dialkyl
carbonate, such as methyl, ethyl, n-propyl or n-butyl carbonate, or diaryl
carbonate,
such as diphenyl or dinaphthyl carbonate, or by reacting of a hydroxy-
terminated
alkylene diol with phosgene or bischoloroformate, in a manner well known to
those
skilled in the art. Non-limiting examples of such polycarbonate polyols
include those
commercially available as RavecarbTM 107 from Enichem S.p.A. (Polimeri Europa)
of
Italy and polyhexylene carbonate diols, about 1000 number average molecular
weight,
such as KM10-1733 polycarbonate diol prepared from hexanediol, available from
Stahl. Examples of other suitable polycarbonate polyols that are commercially
available include KM10-1122, KM10-1667 (prepared from a 50/50 weight percent
mixture of cyclohexane dimethanol and hexanediol) (commercially available from
Stahl
U.S.A. Inc. of Peabody, Massachusetts) and DESMOPHENTm 2020E (commercially
available from Bayer Corn).
[00244] The polycarbonate polyol can be produced by reacting diol, such as
described herein, and a dialkyl carbonate, such as described in U.S. Patent
No.
4,160,853. The polycarbonate polyol can include polyhexamethylene carbonate
such
as HO-(CH2)610-C(0)-0-(C1-12)6h-OH, wherein n is an integer from 4 to 24, or
from 4
to 10, or from 5 to 7.
[00245] Non-limiting examples of polyether polyols include
poly(oxyalkylene)
polyols or polyalkoxylated polyols. Poly(oxyalkylene) polyols can be prepared
in
accordance with known methods. In a non-limiting embodiment, a
poly(oxyalkylene)
polyol can be prepared by condensing an alkylene oxide, or a mixture of
alkylene
oxides, using acid- or base-catalyzed addition with a polyhydric initiator or
a mixture of
polyhydric initiators, such as ethylene glycol, propylene glycol, glycerol,
and sorbitol.
Compatible mixtures of polyether polyols can also be used. As used herein,
"compatible" means that two or more materials are mutually soluble in each
other so
as to essentially form a single phase. Non-limiting examples of alkylene
oxides can
include ethylene oxide, propylene oxide, butylene oxide, amylene oxide,
aralkylene
- 54 -
CA 02647153 2012-12-19
oxides, such as styrene oxide, mixtures of ethylene oxide and propylene oxide.
In
some non-limiting embodiments, polyoxyalkylene polyols can be prepared with
mixtures of alkylene oxide using random or step-wise oxyalkylation. Non-
limiting
examples of such poly(oxyalkylene) polyols include polyoxyethylene polyols,
such as
polyethylene glycol, and polyoxypropylene polyols, such as polypropylene
glycol.
[00246] Other polyether polyols include block polymers such as those having
blocks of ethylene oxide-propylene oxide and/or ethylene oxide-butylene oxide.
In
some non-limiting embodiments, the polyether polyol comprises a block
copolymer of
the following formula:
HO-(CHR, CHR2-0),-(CHR3CHR4-0)b-(CHR5CHR6-0),-H
wherein R1 through R6 can each independently represent hydrogen or methyl; and
a,
b, and c can each be independently selected from an integer from 0 to 300,
wherein a,
b and c are selected such that the number average molecular weight of the
polyol is
less than about 32,000 grams/mole, or less than about 10,000 grams/mole, as
determined by GPC. In other non-limiting embodiments a, b, and c each can be
independently an integer from 1 to 300. In other non-limiting embodiments, R1,
R2,
R5, and R6 can be hydrogen, and R3 and R4 each can be independently selected
from
hydrogen and methyl, with the proviso that R3 and R4 are different from one
another.
In other non-limiting embodiments, R3 and R4 can be hydrogen, and R1 and R2
each
can be independently selected from hydrogen and methyl, with the proviso that
R1 and
R2 are different from one another, and R5 and R6 each can be independently
selected
from hydrogen and methyl, with the proviso that R5 and R6 are different from
one
another.
[00247] In some non-limiting embodiments, polyalkoxylated polyols can be
represented by the following general formula:
OH
m n
R1 R2
Formula (I')
wherein m and n can each be a positive integer, the sum of m and n being from
5 to
70; R1 and R2 are each hydrogen, methyl or ethyl; and A is a divalent linking
group
such as a straight or branched chain alkylene which can contain from 1 to 8
carbon
atoms, phenylene, and C1 to C9 alkyl-substituted phenylene. The values of m
and n
can, in combination with the selected divalent linking group, determine the
molecular
weight of the polyol. Polyalkoxylated polyols can be prepared by methods that
are
- 55 -
CA 02647153 2012-12-19
known in the art. In a non-
limiting embodiment, a polyol such as 4,4'-
isopropylidenediphenol can be reacted with an oxirane-containing material such
as
ethylene oxide, propylene oxide or butylene oxide, to form what is commonly
referred
to as an ethoxylated, propoxylated or butoxylated polyol having hydroxyl
functionality.
Non-limiting examples of polyols suitable for use in preparing polyalkoxylated
polyols
can include those polyols described in U.S. Patent No. 6,187,444 B1 at column
10,
lines 1-20.
[00248] In some non-
limiting embodiments, the polyether polyol can be
PLURONICTM ethylene oxide/propylene oxide block copolymers, such as
PLURONICTM R and PLURONICTM L62D, and/or TETRONICTm tetra-functional block
copolymers based on ethylene oxide and propylene oxide, such as TETRONICTm R,
which are commercially available from BASF Corp. of Parsippany, New Jersey.
[00249] As used
herein, the phrase "polyether polyols" also can include
poly(oxytetramethylene) diols prepared by the polymerization of
tetrahydrofuran in the
presence of Lewis acid catalysts such as but not limited to boron trifluoride,
tin (IV)
chloride and sulfonyl chloride.
Group D
[00250] In some non-
limiting embodiments, the present invention provides
polyurethanes of Group D comprising a reaction product of components
comprising: at
least one polyisocyanate; at least one branched polyol having 4 to 18 carbon
atoms
and at least 3 hydroxyl groups; and at least one polyol having one or more
bromine
atoms, one or more phosphorus atoms or combinations thereof. Brominated or
phosphonated polyols can provide the polyurethane with enhanced flame
retardancy.
The flame retardancy of polyurethanes of the present invention can be
determined
simply by exposure to flame to determine if the polymer is self-extinguishing
or burns
more slowly that a polymer without the brominated or phosphonated polyol, or
according to Underwriter's Laboratory Test UL-94.
[00251] In other non-
limiting embodiments, the present invention provides
polyurethanes of Group D comprising a reaction product of components
consisting of:
about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3 to
about
0.5 equivalents of trimethylolpropane; about 0.2 to about 0.5 equivalents of
bis(4-(2-
hydroxyethoxy)-3,5-dibromophenyl) sulfone; about 0.2 to about 0.5 equivalents
of 1,4-
cyclohexane dimethanol; and about 0.2 to about 0.5 equivalents of 3,6-dithia-
1,2-
octanediol.
- 56 -
CA 02647153 2012-12-19
[00252] Non-limiting
examples of suitable polyisocyanates and branched polyols
having 4 to 18 carbon atoms and at least 3 hydroxyl groups for use in as
reaction
products for preparing the polyurethanes of Group D are discussed in detail
above with
respect to Group A.
[00253] Non-limiting
examples of suitable polyols having one or more bromine
atoms, one or more phosphorus atoms or combinations thereof include 4,4'-
isopropylidene bis(2,6-dibromophenol), isopropylidene
bis[2-(2,6-dibromo-
phenoxy)ethanol], bis(4-(2-hydroxyethoxy)-3,5-dibromophenyl) sulfone
heptakis(dipropylene glycol) triphosphite, tris(dipropylene glycol) phosphate,
diethyl-
N,N-bis(2-hydroxyethyl) aminoethanol phosphonate and mixtures thereof. Non-
limiting
examples of suitable phosphonated polyols include those of the formula HO-Y-
0[POOR-O-Y-0][POOR-0-Y-OH, wherein each R is independently selected from an
alkylene group having 1 to 10 repeat units, such as CH2 to (CH2)10 and each Y
is
independently selected from an alkylene group having 1 to 6 repeat units, such
as CH2
to (CH2)6.
[00254] The amount of
brominated polyols and/or phosphonated polyols used to
form the polyurethane of Group D can be about 0.1 to about 0.9 equivalents, or
about
0.3 to about 0.9 equivalents, or about 0.3 equivalents.
[00255] In some non-
limiting embodiments, the reaction components can further
comprise one or more of the polyether polyols and/or polyester polyols
discussed
above. If present, the amount of polyether polyols and/or polyester polyols
used to
form the polyurethane of Group D can be about 0.1 to about 0.9 equivalents, or
about
0.3 to about 0.9 equivalents, or about 0.3 equivalents.
Groups A-D
[00256] In some non-
limiting embodiments of the polyurethanes of Groups A-D,
the reaction products can further comprise one or more of the following:
polyurethane
polyols, (meth)acrylamides, hydroxy(meth)acrylamides, polyvinyl alcohols,
polymers
containing hydroxy functional (meth)acrylates, polymers containing allyl
alcohols,
polyesteramides and mixtures thereof. In some embodiments, polymerization with
acrylamides can form an interpenetrating network having high transparency,
good
impact strength, and high Young's modulus.
[00257] Non-limiting
examples of suitable polyurethane polyols include the
reaction product of an excess of polyisocyanate and a branched or straight
chain
polyol. The equivalent ratio of polyisocyanate to polyol can range from about
1.0:0.05
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CA 02647153 2012-12-19
to about 1Ø3, or about 1.0:0.7. The amount of polyurethane polyols used can
range
from about 1 to about 90 weight percent, about 5 to about 70 weight percent,
or about
20 to about 50 weight percent on a basis of total weight of the components.
1002581 Non-limiting
examples of suitable acrylamides include acrylamide,
methacrylamide and dimethylacrylamide. The acrylamide can be added with all of
the
other reaction components, or it can be dissolved in the diol and then mixed
with the
other reaction components. The amount of acrylamide used can range from about
5 to
about 70 weight percent, about 10 to about 50 weight percent, or about 10 to
about 30
weight percent on a basis of total weight of the components.
1002591 Non-limiting
examples of suitable polyvinyl alcohols include polyvinyl
alcohol. The amount of polyvinyl alcohol used can range from about 5 to about
90
weight percent, about 10 to about 70 weight percent, or about 10 to about 40
weight
percent on a basis of total weight of the components.
1002601 Non-limiting
examples of suitable polymers containing hydroxy
functional (meth)acrylates include hydroxypropylacrylate;
hydroxyethylacrylate;
hydroxypropylmethacrylate; hydroxyethylmethacrylate; and copolymers of hydroxy
functional (meth)acrylates with acrylamides,
cyanoethyl(meth)acrylates,
methylmethacrylates, methacrylates, ethacrylates,
propylacrylates and
vinylpyrrolidinone. The amount of hydroxy functional (meth)acrylates used can
range
from about 10 to about 90 weight percent, about 10 to about 70 weight percent,
or
about 10 to about 30 weight percent on a basis of total weight of the
components.
1002611 Non-limiting
examples of suitable polymers containing allyl alcohols
include diethylene glycol bis(allylcarbonate), allyloxytrimethylsilane, and
diallylcarbonate. The amount of ally' alcohols used can range from about 5 to
about
70 weight percent, about 10 to about 50 weight percent, or about 10 to about
30
weight percent.
1002621 Non-limiting
examples of suitable polyesteramides include esteramide
polymers obtained by the reaction of bis-oxamidodiols such as N,N'-bis(omega-
hydroxyalkylene)oxamide with a dicarboxylic acid or diester such as diethyl
oxalate,
diethyl succinates, diethyl suberate, or dimethyl terephthalate. The amount
of
polyesteramides used can range from about 10 to about 80 weight percent, about
20
to about 60 weight percent, or about 30 to about 50 weight percent on a basis
of total
weight of the components.
1002631 In some non-
limiting embodiments of the polyurethanes of Groups A-C,
the reaction products can further comprise one or more amine curing agents.
The
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CA 02647153 2012-12-19
amine curing agent, if present, can act as a catalyst in the polymerization
reaction, be
incorporated into the resulting polymerizate and can form poly(ureaurethane)s.
The
amount of amine curing agent used can range from about 0.05 to about 0.9
equivalents, about 0.1 to about 0.7 equivalents, or about 0.3 to about 0.5
equivalents.
[00264] Non-limiting examples of such amine curing agents include aliphatic
polyamines, cycloaliphatic polyamines, aromatic polyamines and mixtures
thereof. In
some non-limiting embodiments, the amine curing agent can have at least two
functional groups selected from primary amine (-NH2), secondary amine (-NH-)
and
combinations thereof. In some non-limiting embodiments, the amine curing agent
can
have at least two primary amine groups. In some non-limiting embodiments, the
amino groups are all primary groups.
[00265] Examples of such amine curing agents include compounds having the
following formula:
R1
FI,
- 100 NH-
2
R2
R3 R3
wherein R1 and R2 are each independently selected from methyl, ethyl, propyl,
and
isopropyl groups, and R3 is selected from hydrogen and chlorine, such as the
following
compounds manufactured by Lonza Ltd. (Basel, Switzerland): LONZACURE M-
DIPA, in which R1=C3 H7; R2=C3 H7; R3=H; LONZACURE OD M-DMA, in which
R1=CH3; R2=CH3; R3=H; LONZACURE OD M-MEA, in which R1=CH3; R2=C2 H5,
R3=H; LONZACURE OD M-DEA, in which R1=C2 H5; R2=C2 H5; R3=H; LONZACURE
M-MIPA,: in which R1=CH3; R2=C3 H7; R3=1-1, and LONZACURE M-CDEA, in which
R1=C2 H5; R2=C2 H5; R3=CI, each of which is commercially available from Air
Products and Chemicals, Inc. of Allentown, PA.
[00266] Such amine curing agents can include a diamine curing agent such as
4,4'-methylenebis(3-chloro-2,6-diethylaniline), (LONZACURE M-CDEA); 2,4-
diamino-3,5-diethyl-toluene, 2,6-diamino-3,5-diethyl-toluene and mixtures
thereof
(collectively "diethyltoluenediamine" or "DETDA"), which is commercially
available
from Albemarle Corporation under the trade name ETHACURETm 100;
dimethylthiotoluenediamine (DMTDA) (commercially available as ETHACURETm 300);
the color stabilized version of ETHACURETm 100 (i.e., formulation which
contains an
- 59 -
CA 02647153 2012-12-19
additive to reduce yellow color), which is available under the name ETHACURETm
100S; 4,4'-methylene-bis-(2-chloroaniline) (commercially available from
Kingyorker
Chemicals under the trade name MOCA). DETDA can be a liquid at room
temperature
with a viscosity of 156 centipoise (cp) at 25 C. DETDA can be isomeric, with
the 2,4-
isomer amount being from 75 to 81 percent while the 2,6-isomer amount can be
from
18 to 24 percent.
1002671 Other non-
limiting examples of amine curing agents include
ethyleneamines, such as ethylenediamine (EDA), diethylenetriamine (DETA),
triethylenetetramine (TETA), tetraethylenepentamine (TEPA),
pentaethylenehexamine
(PEHA), piperazine, morpholine, substituted morpholine, piperidine,
substituted
piperidine, diethylenediamine (DEDA), and 2-amino-1-ethylpiperazine. In some
non-
limiting embodiments, the amine curing agent can be selected from one or more
isomers of C1-C3 dialkyl toluenediamine, such as 3,5-dimethy1-2,4-
toluenediamine,
3 ,5-dimethy1-2 ,6-tol uened iamine, 3,5-d iethy1-2
,4-toluened iamine , 3 ,5-diethyl-2 ,6-
toluenediamine, 3,5-diisopropy1-2,4-toluenediamine,
3,5-diisopropy1-2,6-
toluenediamine, and mixtures thereof. In some non-limiting embodiments, the
amine
curing agent can be methylene dianiline or trimethyleneglycol di(para-
aminobenzoate).
[00268] Other non-
limiting examples of amine curing agents include compounds
of the following general structures (XIII-XV):
H2 H2
(XIII)
H2N NH2
(XIV)
S
H2N I\TH2
(XV)
1002691 Other non-
limiting examples of amine curing agents include one or
more methylene bis anilines represented by the general formulas XVI-XX, one or
more
aniline sulfides represented by the general formulas XXI-XXV, and/or one or
more
bianilines represented by the general formulas XXVI-XXVIX,
- 60 -
CA 02647153 2012-12-19
R3 R3
H2N
abh NH2
( XVI )
R4
R4
.5
R3 NH2
H2N
R4
(XVII)
R4 R5
.5 .5
2 NH2
(XVIII)
R5
s.: R4
R5
.5
5
.3 .5
H2N
(XIX)
R3
R4 NH2
NH2 R5
R4
( XX )
R3
R5 NH2
5
H2 NH2
(XXI)
R4
R5 a R5
'5 '5
- 61 -
- Z9 -
c-,a g1 g
A ill
ill
0 0
HM (IIAXX)
ZFIN
tH s. s. 17H
zHN
0 0 HM (IAXX)
g. gIl .
. C.
zHN S la cll
qi 11111 IIIPP H (AXX)
t
5= zHN
t . s .
z HN
S 1711
EN $ 0 (AIXX)
Nzli
sli E.
S. S.
SN
S III
NzH (Iiixx)
41N1 -la
c. c.
17x S 1711
* . (IIxx)
zHN NzH
cc
. I
61-ZT-ZTOZ ESTLV9Z0 VD
CA 02647153 2012-12-19
NH2 R3 3 NH2
(XXVIII) R4
R4
R5 = 5 = 5 R5
. 5
R5 3 NH2
(XXIX) R3
R4
N 2 '4'5 R5
wherein R3 and R4 are each independently C1-C3 alkyl, and R5 is selected from
hydrogen and halogen, such as chlorine or bromine. The diamine represented by
general formula XV can be described generally as a 4,4'-methylene-
bis(dialkylaniline).
Suitable non-limiting examples of diamines which can be represented by general
formula XV include but are not limited to 4,4'-methylene-bis(2,6-
dimethylaniline), 4,4'-
methylene-bis(2,6-diethylaniline), 4,4'-methylene-bis(2-ethyl-6-
methylaniline), 4,4'-
methylene-bis(2,6-diisopropylaniline), 4,4'-methylene-bis(2-isopropyl-6-
methylaniline)
and 4,4'-methylene-bis(2,6-diethyl-3-chloroaniline).
1002701 The amine curing agent includes compounds represented by the
following general structure ()(XX):
NH2
R23 R20
(XXX )
0
R22 NH2
.27
where R20, R21, R22, and R23 are each independently selected from H, C1-C3
alkyl,
CH3-S- and halogen, such as chlorine or bromine. The amine curing agent
represented by general formula XXX can include diethyl toluene diamine (DETDA)
wherein R23 is methyl, R20 and R21 are each ethyl and R22 is hydrogen. Also,
the
amine curing agent can include 4,4'-methylenedianiline.
1002711 In an embodiment wherein it is desirable to produce a
poly(ureaurethane) having low color, the amine curing agent can be selected
such that
it has relatively low color and/or it can be manufactured and/or stored in a
manner as
to prevent the amine from developing a color (e.g., yellow).
- 63 -
CA 02647153 2012-12-19
[00272] In some non-limiting embodiments of the polyurethanes of Groups A-
D,
the reaction products can be essentially free of amine curing agent. As used
herein,
"essentially free of amine curing agent" means that the reaction product
components
comprise less than about 10 weight percent of amine curing agent, or less than
about
weight percent of amine curing agent, or less than about 2 weight percent of
amine
curing agent, or in other non-limiting embodiments are free of amine curing
agent.
Group E
[00273] In some non-limiting embodiments, the present invention provides
polyurethanes of Group E comprising a reaction product of components
comprising:
about 1 equivalent of at least one polyisocyanate; about 0.3 to about 1
equivalents of
at least one branched polyol having 4 to 18 carbon atoms and at least 3
hydroxyl
groups; and about 0.01 to about 0.3 equivalents of at least one polycarbonate
diol,
wherein the reaction product components are essentially free of polyether
polyol and
amine curing agent and wherein the reaction components are maintained at a
temperature of at least about 100 C for at least about 10 minutes.
[00274] Non-limiting examples of suitable polyisocyanates, branched polyols
having 4 to 18 carbon atoms and at least 3 hydroxyl groups, polycarbonate
diols and
diol having 2 to 18 carbon atoms for use in as reaction products for preparing
the
polyurethanes of Group E are discussed in detail above with respect to Group
A.
[00275] In some non-limiting embodiments, the amount of branched polyol
used
to form the polyurethane of Group E can range from about 0.3 to about 0.98
equivalents, or about 0.5 to about 0.98 equivalents, or about 0.3 equivalents
or about
0.9 to about 0.98 equivalents.
[00276] In some non-limiting embodiments, the amount of polycarbonate diol
used to form the polyurethane of Group E can range from about 0.01 to about
0.1
equivalents, or about 0.05 to about 0.1 equivalents, or about 0.1 equivalents.
[00277] In another embodiment, the present invention provides polyurethanes
of
Group E comprising a reaction product of components consisting of: about 1
equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3
equivalents of
trimethylolpropane; about 0.55 equivalents of 1,5-pentanediol and about 0.15
equivalents of KM10-1733 polycarbonate diol prepared from hexanediol,
available
from Stahl, wherein the reaction components are maintained at a temperature of
at
least about 100 C for at least about 10 minutes.
- 64 -
CA 02647153 2012-12-19
[00278] In another embodiment, the present invention provides polyurethanes
of
Group E comprising a reaction product of components consisting of: about 1
equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3
equivalents of
trimethylolpropane; about 0.5 equivalents of 1,5-pentanediol and about 0.2
equivalents
of KM10-1733 polycarbonate diol prepared from hexanediol, available from
Stahl,
wherein the reaction components are maintained at a temperature of at least
about
100 C for at least about 10 minutes.
[00279] The polyurethanes of Group E can exhibit good ballistics
resistance.
[00280] The polyurethanes of Group E are essentially free of polyether
polyol
and amine curing agent, the types and amounts of polyether polyol and amine
curing
agent being described above with respect to Groups A-D.
[00281] In some non-limiting embodiments of the polyurethanes of Group E,
the
reaction products can further comprise one or more of the following:
polyurethane
polyols, acrylamides, polyvinyl alcohols, polymers containing hydroxy
functional
(meth)acrylates, polymers containing allyl alcohols, polyesteramides and
mixtures
thereof, as described and in amounts as above with respect to Groups A-D.
- 65 -
CA 02647153 2012-12-19
Group F
[00282] In some non-limiting embodiments, the present invention provides
polyurethanes of Group F comprising a reaction product of components
comprising:
(a) about 1 equivalent of at least one polyisocyanate; (b) about 0.3 to about
1
equivalents of at least one branched polyol having 4 to 18 carbon atoms and at
least 3
hydroxyl groups; (c) about 0.01 to about 0.3 equivalents of at least one
polycarbonate
diol; and (d) about 0.1 to about 0.9 equivalents of at least one diol having 2
to 18
carbon atoms, wherein the reaction product components are essentially free of
polyether polyol and wherein the reaction components are maintained at a
temperature of at least about 100 C for at least about 10 minutes. The diol
having 2 to
18 carbon atoms is chemically different from the polycarbonate diol, e.g., the
diol has
at least one different atom or a different arrangement of atoms compared to
the
polycarbonate diol.
[00283] Non-limiting examples of suitable polyisocyanates, branched polyols
having 4 to 18 carbon atoms and at least 3 hydroxyl groups, polycarbonate
diols and
diol having 2 to 18 carbon atoms for use in as reaction products for preparing
the
polyurethanes of Group F are discussed in detail above with respect to Group
A.
[00284] In some non-limiting embodiments, the amount of branched polyol
used
to form the polyurethane of Group F can range from about 0.3 to about 0.98
equivalents, or about 0.5 to about 0.98 equivalents, or about 0.9 to about
0.98
equivalents.
[00285] In some non-limiting embodiments, the amount of polycarbonate diol
used to form the polyurethane of Group F can range from about 0.01 to about
0.1
equivalents, or about 0.05 to about 0.1 equivalents, or about 0.1 equivalents.
[00286] In some non-limiting embodiments, the amount of diol used to form
the
polyurethane of Group F can range from about 0.01 to about 0.1 equivalents, or
about
0.05 to about 0.1 equivalents, or about 0.1 equivalents.
[00287] The polyurethanes of Group F are essentially free of polyether
polyol,
the types and amounts of polyether polyol being described above with respect
to
Groups A-D.
1002881 In some non-limiting embodiments of the polyurethanes of Group F,
the
reaction products can further comprise one or more of the following:
polyurethane
polyols, acrylamides, polyvinyl alcohols, polymers containing hydroxy
functional
(meth)acrylates, polymers containing allyl alcohols, polyesteramides and
mixtures
thereof, as described and in amounts as above with respect to Groups A-D.
- 66 -
CA 02647153 2012-12-19
[00289] In some non-limiting embodiments of the polyurethanes of Group F,
the
reaction products can further comprise one or more amine curing agents as
discussed
above with respect to Group E. In other non-limiting embodiments, the reaction
products for preparing the polyurethanes of Group F can be essentially free of
or free
of amine curing agent as discussed above with respect to Groups A-D.
Group G
[00290] In some non-limiting embodiments, the present invention provides
polyurethanes of Group G comprising a reaction product of components
comprising:
about 1 equivalent of at least one polyisocyanate; about 0.3 to about 1
equivalents of
at least one branched polyol having 4 to 18 carbon atoms and at least 3
hydroxyl
groups; about 0.01 to about 0.3 equivalents of at least one polyol selected
from the
group consisting of polyester polyol, polycaprolactone polyol and mixtures
thereof; and
about 0.1 to about 0.7 equivalents of at least one aliphatic diol, wherein the
reaction
product components are essentially free of polyether polyol and amine curing
agent
and wherein the reaction components are maintained at a temperature of at
least
about 100 C for at least about 10 minutes, wherein the reaction components are
maintained at a temperature of at least about 100 C for at least about 10
minutes.
[00291] Non-limiting examples of suitable polyisocyanates, branched polyols
having 4 to 18 carbon atoms and at least 3 hydroxyl groups, polyester polyols,
polycaprolactone polyols and aliphatic diols for use as reaction products for
preparing
the polyurethanes of Group G are discussed in detail above with respect to
Group A.
The aliphatic diol is chemically different from the polyester polyol and
polycaprolactone
polyol, e.g., the diol has at least one different atom or a different
arrangement of atoms
compared to the polyester polyol and polycaprolactone polyol.
[00292] In some non-limiting embodiments, the amount of branched polyol
used
to form the polyurethane of Group G can range from about 0.3 to about 0.9
equivalents, or about 0.3 to about 0.7 equivalents, or about 0.4 equivalents
to about
0.6 equivalent, or about 0.7 equivalents.
[00293] In some non-limiting embodiments, the amount of polyester and/or
polycaprolactone polyol used to form the polyurethane of Group GF can range
from
about 0.01 to about 0.1 equivalents, or about 0.05 to about 0.1 equivalents,
or about
0.1 equivalents.
- 67 -
CA 02647153 2012-12-19
1002941 In some non-limiting embodiments, the amount of aliphatic diol used
to
form the polyurethane of Group G can range from about 0.1 to about 0.6
equivalents,
or about 0.1 to about 0.5 equivalents, or about 0.5 equivalents.
[00295] The polyurethanes of Group G are essentially free of or free of
polyether polyol and/or amine curing agent, the types and amounts of polyether
polyol
and amine curing agent being described above with respect to Groups A-D.
[00296] In some non-limiting embodiments of the polyurethanes of Group G,
the
reaction products can further comprise one or more of the following:
polyurethane
polyols, acrylamides, polyvinyl alcohols, polymers containing hydroxy
functional
(meth)acrylates, polymers containing ally' alcohols, polyesteramides and
mixtures
thereof, as described and in amounts as above with respect to Groups A-D.
[00297] In other non-limiting embodiments, the present invention provides
polyurethanes of Group G comprising a reaction product of components
consisting of:
about 1 equivalent of 4,4'-methylene-bis-(cyclohexyl isocyanate); about 0.3
equivalents of trimethylolpropane; about 0.5 equivalents of decanediol; and
about 0.2
equivalents of polycaprolactone polyol, such as Dow TONETm 0210
polycaprolactone
polyol having a number average molecular weight of about 1000 grams/mole,
wherein
the reaction components are maintained at a temperature of at least about 100
C for
at least about 10 minutes.
[00298] In other non-limiting embodiments, the present invention provides
polyurethanes of Group G prepared from a prepolymer which is the reaction
product of
components comprising: (1) about 0.4 equivalents of 4,4'-methylene-bis-
(cyclohexyl
isocyanate) (such as DESMODURTm VV); (2) about 0.3 equivalents of
polycaprolactone
diol (such as CAPATM 2047 and CAPATM 2077A polycaprolactone diols prepared
from
hexanediol); (3) about 0.05 equivalents of trimethylolpropane. The prepolymer
is
reacted with at least one aliphatic diol having 2 to 18 carbon atoms as
described
above, such as butanediol or pentanediol.
Group H
[00299] In other non-limiting embodiments, the present invention provides
polyurethanes of Group H comprising a reaction product of components
comprising:
(a) a prepolymer which is the reaction product of components comprising: (1)
at least
one polyisocyanate; (2) at least one polycaprolactone polyol; and (3) at least
one
polyol selected from the group consisting of polyalkylene polyol, polyether
polyol and
mixtures thereof; and (b) at least one diol having 2 to 18 carbon atoms.
- 68 -
CA 02647153 2012-12-19
[00300] Non-limiting
examples of suitable polyisocyanates, polycaprolactone
polyols, polyalkylene polyols, polyether polyols and diols having 2 to 18
carbon atoms
for use as reaction products for preparing the polyurethanes of Group H are
discussed
in detail above with respect to Group A. Non-limiting
examples of suitable
polyalkylene polyols include polyethylene glycols, polypropylene glycols and
mixtures
thereof. The polyalkylene glycol can have a number average molecular weight
ranging
from about 200 to about 1000 grams/mole, or from about 200 grams/mole to about
4,000 grams/mole.
[00301] The diol is
chemically different from the polyalkylene polyol and
polyether polyol, e.g., the diol has at least one different atom or a
different
arrangement of atoms compared to the polyalkylene polyol and polyether polyol.
[00302] In some non-
limiting embodiments, the amount of branched
polycaprolactone polyol used to form the polyurethane of Group H can range
from
about 0.05 to about 0.8 equivalents, or about 0.1 to about 0.6 equivalents, or
about 0.1
equivalents to about 0.4 equivalent, or about 0.3 equivalents.
[00303] In some non-
limiting embodiments, the amount of polyalkylene polyol
and/or polyether polyol used to form the polyurethane of Group H can range
from
about 0.1 to about 0.9 equivalents, or about 0.2 to about 0.6 equivalents, or
about 0.4
equivalents.
[00304] In some non-
limiting embodiments, the amount of diol used to form the
polyurethane of Group H can range from about 0.1 to about 0.9 equivalents, or
about
0.3 to about 0.8 equivalents, or about 0.7 equivalents.
[00305] The
polyurethanes of Group H are prepared by reacting reaction
product components comprising: (1) at least one polyisocyanate; (2) at least
one
polycaprolactone polyol; and (3) at least one polyol selected from the group
consisting
of polyalkylene polyol, polyether polyol and mixtures thereof to form a
prepolymer.
The prepolymer is then reacted with at least one diol having 2 to 18 carbon
atoms and
any other optional reaction components as described below.
[00306] In some non-
limiting embodiments of the polyurethanes of Group H, the
reaction products can further comprise one or more of the following: branched
polyols
having at lest three hydroxyl groups, polyurethane polyols, acrylamides,
polyvinyl
alcohols, polymers containing hydroxy functional (meth)acrylates, polymers
containing
allyl alcohols, polyesteramides and mixtures thereof, as described and in
amounts as
above with respect to Groups A-D.
- 69 -
CA 02647153 2012-12-19
[00307] In some non-limiting embodiments of the polyurethanes of Group H,
the
reaction products can further comprise one or more amine curing agents as
discussed
above with respect to Group E. In other non-limiting embodiments, the reaction
products for preparing the polyurethanes of Group H can be essentially free of
or free
of amine curing agent as discussed above with respect to Groups A-D.
[00308] In other non-limiting embodiments, the present invention provides
polyurethanes of Group H comprising a reaction product of components
comprising:
(a) a prepolymer which is the reaction product of components comprising: (1)
aliphatic
or cycloaliphatic diisocyanate; (2) polycaprolactone diol; (3) polyethylene
glycol; and
(4) polyoxyethylene and polyoxypropylene copolymer and (b) at least one diol
having 2
to 18 carbon atoms.
[00309] In other non-limiting embodiments, the present invention provides
polyurethanes of Group H prepared from a prepolymer which is the reaction
product of
components comprising: (1) about 0.4 equivalents of 4,4'-methylene-bis-
(cyclohexyl
isocyanate) (such as DESMODURTm VV); (2) about 0.003 equivalents of
polycaprolactone diol (such as CAPATM 2077A polycaprolactone diol prepared
from
hexanediol); (3) about 0.025 equivalents of polyethylene glycol (such as
PLURACOLTM
E400NF); (4) about 0.029 equivalents of polyoxyethylene and polyoxypropylene
copolymer (such as PLURONICTM L62D ethylene oxide/propylene oxide block
copolymer); (5) about 0.05 equivalents of trimethylolpropane; and additives
such as
catalyst (for example dibutyltin dilaurate), antioxidant (such as IRGANOXTM
1010 and
IRGANOXTM MD 1024), and ultraviolet light stabilizer(s) such as CYASORBTM UV
5411 and TINUVINTm 328 (each described below).
[00310] The isocyanate-terminated prepolymer is reacted with at least one
diol
having 2 to 18 carbon atoms, such as 1,4-butanediol and/or 1,4-cyclohexane
dimethanol in an equivalent ratio of about 0.75:0.25 1,4-butanediol to 1,4-
cyclohexane
dimethanol. The equivalent ratio of prepolymer to diol is about 1:1.
Groups A-H
[00311] Referring now to the inventions of Groups A-H, the polyurethanes of
the
present invention can be polymerized using a variety of techniques. In some
non-
limiting embodiments described in further detail below, polyisocyanate and
polyol can
be reacted together in a one-pot process to form the polyurethane. Sulfur-
containing
polyurethanes of the present invention can be produced by combining isocyanate
and/or isothiocyanate and polyol and/or polythiol.
- 70 -
CA 02647153 2012-12-19
[00312] In other non-
limiting embodiments, the polyurethane can be prepared
by reacting polyisocyanate(s) and polyol(s) to form a polyurethane prepolymer
and
then introducing diol(s), and optionally catalyst and other optional reaction
components.
[00313] In other non-
limiting embodiments such as Group B, the polyurethane
can be prepared by reacting polyisocyanate(s) and diol(s) to form an
isocyanate
functional urethane prepolymer and then introducing diol(s), polyols and
optionally
catalyst and other optional reaction components. In some
embodiments, the
isocyanate functional urethane prepolymer, polyol and second portion of diol
reaction
components are maintained at a temperature of at least about 100 C for at
least about
minutes, or at least about 110 C for at least about 10 minutes or 20 minutes.
[00314] Whether
prepared in a one-shot process or in a multi-stage process
using a prepolymer, in some non-limiting embodiments, the aforementioned
ingredients each can be degassed prior to reaction. In some non-
limiting
embodiments, the prepolymer can be degassed, the difunctional material can be
degassed, and then these two materials can be combined.
[00315] In the "one
shot" or bulk polymerization method, all of the ingredients,
that is, isocyanate, polyol and diol are mixed simultaneously. This method is
generally
satisfactory when all active hydrogens react at about the same rate such as
when all
contain hydroxyl groups as the only reactive sites. The urethane reaction can
be
conducted under anhydrous conditions with dry reactants such as in a nitrogen
atmosphere of atmospheric pressure and at a temperature ranging from about 75
C to
about 140 C. If polycarbonate polyols or any hydroxy functional compounds are
used,
they are typically dried before reaction, usually to a moisture content
ranging from
about 0.01 to about 0.05 percent.
1003161 To obtain the
randomness desired and a generally clear polymer, the
diol, for example, anhydrous 1,4-butanediol (containing a maximum of 0.04
percent
water) can be added to the polyol under a nitrogen atmosphere to exclude
moisture
and the temperature maintained sufficiently high so that there is no phase
separation
and a homogeneous mixture is obtained. The polyisocyanate, for example, 4,4'-
methylene-bis-(cyclohexyl isocyanate), can be added rapidly and the mixture
can be
maintained at a temperature of at least about 75 C, or at least about 85 C, or
at least
about 90 C, or at least about 95 C for at least about 10 minutes or at least
about 20
minutes. In some embodiments, the mixture is maintained at a temperature of at
least
about 100 C, or at least about 105 C, or at least about 110 C for at least
about 10
- 71 -
CA 02647153 2012-12-19
minutes or at least about 20 minutes, so that there is no phase separation and
the
mixture remains homogeneous. The mixture can be maintained at a pressure of
ranging from about 2 to about 6 mm Hg (about 266.6 to about 800 Pascal (Pa)),
or
about 266.6 Pa for a time period of about 10 minutes to about 24 hours, or
about 10
minutes to about 4 hours.
[00317] In some non-limiting embodiments, the mixture can be vigorously
agitated at a temperature of at least about 75 C, or at least about 85 C, or
at least
about 90 C, or at least about 95 C, or at least about 100 C, or at least about
105 C, or
at least about 110 C, and degassed for a period of at least about 3 minutes
during
which time the pressure is reduced from atmospheric to about 3 millimeters of
mercury. The reduction in pressure facilitates the removal of the dissolved
gases such
as nitrogen and carbon dioxide and then the ingredients can be reacted at a
temperature ranging from about 100 C to about 140 C, or about 110 C to about
140 C, in the presence of a catalyst and the reaction continued until there
are
substantially no isocyanate groups present, in some embodiments for at least
about 6
hours. In the absence of a catalyst, the reaction can be conducted for at
least about
24 hours, such as under a nitrogen atmosphere.
[00318] In some non-limiting embodiments, wherein a window can be formed,
the polymerizable mixture which can be optionally degassed can be introduced
into a
mold and the mold can be heated (i.e., thermal cure cycle) using a variety of
conventional techniques known in the art. The thermal cure cycle can vary
depending
on the reactivity and molar ratio of the reactants. In a non-limiting
embodiment, the
thermal cure cycle can include heating the mixture of prepolymer and diol and
optionally diol and dithiol; or heating the mixture of polyisocyanate, polyol
and/or
polythiol and diol or diol/dithiol, from room temperature to a temperature of
about
200 C over a period of from about 0.5 hours to about 72 hours; or from about
80 C to
about 150 C for a period of from about 5 hours to about 48 hours.
[00319] In other non-limiting embodiments described in further detail
below,
isocyanate and polyol can be reacted together to form a polyurethane
prepolymer and
the prepolymer can be reacted with more of the same or a different polyol(s)
and/or
diol(s) to form a polyurethane or sulfur-containing polyurethane. When the
prepolymer
method is employed, the prepolymer and diol(s) can be heated so as to reduce
the
prepolymer viscosity to about 200 cp or at most a few thousand centipoise so
as to aid
in mixing. As in the bulk polymerization, reaction should be conducted under
anhydrous conditions with dry reactants.
- 72 -
CA 02647153 2012-12-19
[00320] The polyurethane prepolymer can have a number average molecular
weight (Mn) of less than about 50,000 grams/mole, or less than about 20,000
grams/mole, or less than about 10,000 grams/mole, or less than about 5,000
grams/mole, or at least about 1,000 grams/mole or at least about 2,000
grams/mole,
inclusive of any range in between.
[00321] When polyurethane-forming components, such as polyols and
isocyanates, are combined to produce polyurethanes, the relative amounts of
the
ingredients are typically expressed as a ratio of the available number of
reactive
isocyanate groups to the available number of reactive hydroxyl groups, i.e.,
an
equivalent ratio of NCO:OH. For example, a ratio of NCO:OH of 1.0:1.0 is
obtained
when the weight of one NCO equivalent of the supplied form of the isocyanate
component is reacted with the weight of one OH equivalent of the supplied form
of the
organic polyol component. The polyurethanes of the present invention can have
an
equivalent ratio of NCO:OH ranging from about 0.9:1.0 to about 1.1:1.0, or
about
1.0:1Ø
[00322] In some non-limiting embodiments, when the isocyanate and polyol
are
reacted to form a prepolymer, the isocyanate is present in excess, for example
the
amount of isocyanate and the amount of polyol in the isocyanate prepolymer can
be
selected such that the equivalent ratio of (NCO):(OH) can range from about
1.0: 0.05
to about 1.0:0.7.
[00323] In some non-limiting embodiments, the amount of isocyanate and the
amount of polyol used to prepare isocyanate-terminated polyurethane prepolymer
or
isocyanate-terminated sulfur-containing polyurethane prepolymer can be
selected
such that the equivalent ratio of (NCO):(SH + OH) can be at least about
1.0:1.0, or at
least about 2.0:1.0, or at least about 2.5:1.0, or less than about 4.5:1.0, or
less than
about 5.5:1.0; or the amount of isothiocyanate and the amount of polyol used
to
prepare isothiocyanate-terminated sulfur-containing polyurethane prepolymer
can be
selected such that the equivalent ratio of (NCS):(SH + OH) can be at least
about
1.0:1.0, or at least about 2.0:1.0, or at least about 2.5:1.0, or less than
about 4.5:1.0,
or less than about 5.5:1.0; or the amount of a combination of isothiocyanate
and
isocyanate and the amount of polyol used to prepare isothiocyanate/isocyanate
terminated sulfur-containing polyurethane prepolymer can be selected such that
the
equivalent ratio of (NCS + NCO):(SH + OH) can be at least about 1.0:1.0, or at
least
about 2.0:1.0, or at least about 2.5:1.0, or less than about 4.5:1.0, or less
than about
5.5:1.0
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CA 02647153 2012-12-19
[00324] The ratio and
proportions of the diol and the polyol can affect the
viscosity of the prepolymer. The viscosity of such prepolymers can be
important, for
example when they are intended for use with coating compositions, such as
those for
flow coating processes. The solids content of such prepolymers, however, also
can be
important, in that higher solids content can achieve desired properties from
the
coating, such as weatherability, scratch resistance, etc. In conventional
coatings,
coating compositions with higher solids content typically require greater
amounts of
solvent material to dilute the coating in order to reduce the viscosity for
appropriate
flow coating processes. The use of such solvents, however, can adversely
affect the
substrate surface, particularly when the substrate surface is a polymeric
material. In
the present invention, the viscosity of the prepolymer can be appropriately
tailored to
provide a material with lower viscosity levels at higher solids content,
thereby providing
an effective coating without the need for excessive amounts of solvents which
can
deleteriously affect the substrate surface.
[00325] In some non-
limiting embodiments in which optional amine curing agent
is used, the amount of isocyanate-terminated polyurethane prepolymer or sulfur-
containing isocyanate-terminated polyurethane prepolymer and the amount of
amine
curing agent used to prepare sulfur-containing polyurethane can be selected
such that
the equivalent ratio of (NH + SH + OH) : (NCO) can range from about 0.80:1.0
to about
1.1:1.0, or from about 0.85:1.0 to about 1.0:1.0, or from about 0.90:1.0 to
about
1.0:1.0, or from about 0.90:1.0 to about 0.95:1.0, or from about 0.95:1.0 to
about
1.0:1Ø
[00326] In some non-
limiting embodiments, the amount of isothiocyanate or
isothiocyanate/isocyanate terminated sulfur-containing polyurethane prepolymer
and
the amount of amine curing agent used to prepare sulfur-containing
polyureaurethane
can be selected such that the equivalent ratio of (NH + SH + OH) : (NCO + NCS)
can
range from about 0.80:1.0 to about 1.1:1.0, or from about 0.85:1.0 to about
1.0:1.0, or
from about 0.90:1.0 to about 1.0:1.0, or from about 0.90:1.0 to about
0.95:1.0, or from
about 0.95:1.0 to about 1.0:1Ø
[00327] It is believed
that the unusual energy absorption properties and
transparency of the polyurethanes of the present invention may not only be
dependent
upon the urethane ingredients and proportions, but also may be dependent on
the
method of preparation. More
particularly, it is believed that the presence of
polyurethane regular block segments may adversely affect the polyurethane
transparency and energy absorption properties and consequently it is believed
that
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CA 02647153 2012-12-19
random segments within the polymer can provide optimal results. Consequently,
whether the urethane contains random or regular block segments depends upon
the
particular reagents and their relative reactivity as well as the conditions of
reaction.
Generally speaking, the polyisocyanate will be more reactive with a low
molecular
weight diol or polyol, for example, 1,4-butanediol, than with a polymeric
polyol and,
hence, in some non-limiting embodiments it is desirable to inhibit the
preferential
reaction between the low molecular weight diol or polyol and the
polyisocyanate such
as by rapidly adding the polyisocyanate to an intimate mixture of the low
molecular
weight diol or polyol and polymeric polyol with vigorous agitation, such as at
a
temperature of at least about 75 C when no catalyst is employed, and then
maintained
at temperature of reaction of at least about 100 C or about 110 C after the
exotherm
has subsided. When a catalyst is employed, the initial mixing temperature can
be
lower, such as about 60 C, so that the exotherm does not carry the temperature
of the
mixture substantially above the reaction temperature desired. Inasmuch as the
polyurethanes are thermally stable, however, reaction temperatures can reach
as high
as about 200 C and as low as about 60 C, and in some non-limiting embodiments
ranging from about 75 C to about 130 C when a catalyst is employed, or ranging
from
about 80 C to about 100 C. When no catalyst is employed, in some non-limiting
embodiments the reaction temperature can range from about 130 C to about 150
C.
[00328] It is also desirable to rapidly attain reaction temperatures after
a
homogeneous mixture is obtained when a catalyst is not employed, so that the
polymer does not become hazy due to phase separation. For example, some
mixtures
can become hazy in less than one-half hour at less than 80 C without catalyst.
Thus,
it can be desirable either to use a catalyst or introduce the reactants to
rapidly reach a
reaction temperature above about 100 C, or about 110 C or about 130 C, for
example
by the use of a high-speed shear mixing head, so that the polymer does not
become
hazy. Suitable catalysts can be selected from those known in the art. In some
non-
limiting embodiments, degassing can take place prior to or following addition
of
catalyst.
1003291 In some non-limiting embodiments, a urethane-forming catalyst can
be
used in the present invention to enhance the reaction of the polyurethane-
forming
materials. Suitable urethane-forming catalysts include those catalysts that
are useful
for the formation of urethane by reaction of the NCO and OH-containing
materials, and
which have little tendency to accelerate side reactions leading to allophonate
and
isocyanate formation. Non-limiting examples of suitable catalysts are selected
from
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CA 02647153 2012-12-19
the group of Lewis bases, Lewis acids and insertion catalysts as described
in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, 1992, Volume
A21, pp.
673 to 674.
[00330] In some non-
limiting embodiments, the catalyst can be a stannous salt
of an organic acid, such as stannous octoate or butyl stannoic acid. Other
non-
limiting examples of suitable catalysts include tertiary amine catalysts,
tertiary
ammonium salts, tin catalysts, phosphines or mixtures thereof. In some non-
limiting
embodiments, the catalysts can be dimethyl cyclohexylamine, dibutyl tin
dilaurate,
dibutyltin diacetate, dibutyltin mercaptide, dibutyltin diacetate, dibutyl tin
dimaleate,
dimethyl tin diacetate, dimethyl tin dilaurate, 1,4-diazabicyclo[2.2.2]octane,
bismuth
carboxylates, zirconium carboxylates, zinc octoate, ferric acetylacetonate and
mixtures
thereof. The amount of catalyst used can vary depending on the amount of
components, for example about 10 ppm to about 600 ppm.
[00331] In alternate
non-limiting embodiments, various additives can be
included in compositions comprising the polyurethane(s) of the present
invention.
Such additives include light stabilizers, heat stabilizers, antioxidants,
colorants, fire
retardants, ultraviolet light absorbers, light stabilizers such as hindered
amine light
stabilizers, mold release agents, static (non-photochromic) dyes, fluorescent
agents,
pigments, surfactants, flexibilizing additives, such as but not limited to
alkoxylated
phenol benzoates and poly(alkylene glycol) dibenzoates, and mixtures thereof.
Non-
limiting examples of anti-yellowing additives include 3-methyl-2-butenol,
organo
pyrocarbonates and triphenyl phosphite (CAS Registry No. 101-02-0). Examples
of
useful antioxidants include IRGANOXTM 1010, IRGANOXTM 1076, and IRGANOXTM
MD 1024, each commercially available from Ciba Specialty Chemicals of
Tarrytown,
New York. Examples of useful UV absorbers include CYASORBTM UV 5411,
TINUVINTm 130 and TINUVINTm 328 commercially available Ciba Specialty
Chemicals,
and SANDOVARTM 3206 commercially available from Clariant Corp. of Charlotte,
North Carolina. Examples of
useful hindered amine light stabilizers include
SANDOVARTM 3056 commercially available from Clariant Corp. of Charlotte, North
Carolina Examples of useful surfactants include BYK 306 commercially available
from
BYK Chemie of Wesel, Germany.
1003321 Such additives
can be present in an amount such that the additive
constitutes less than about 30 percent by weight, or less than about 15
percent by
weight, or less than about 5 percent by weight, or less than about 3 percent
by weight,
based on the total weight of the polymer. In some non-limiting embodiments,
the
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CA 02647153 2012-12-19
aforementioned optional additives can be pre-mixed with the polyisocyanate(s)
or
isocyanate functional prepolymer. In other non-limiting embodiments, the
optional
additives can be pre-mixed with the polyol(s) or urethane prepolymer.
[00333] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group A comprising the step of reacting
in a
one pot process components comprising: about 1 equivalent of at least one
polyisocyanate; about 0.1 to about 0.9 equivalents of at least one branched
polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and about 0.1 to
about
0.9 equivalents of at least one diol having 2 to 18 carbon atoms, wherein the
components are essentially free of polyester polyol and polyether polyol.
[00334] In other non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group A comprising the steps of:
reacting at
least one polyisocyanate and at least one branched polyol having 4 to 18
carbon
atoms and at least 3 hydroxyl groups to form a polyurethane prepolymer; and
reacting
the polyurethane prepolymer with at least one diol having 2 to 18 carbon atoms
to form
the polyurethane.
In other non-limiting embodiments, the present invention provides methods of
preparing polyurethanes of Group B comprising the steps of:
(a) reacting (i) about 1 equivalent of at least one polyisocyanate; and
(ii)
about 0.1 to about 0.5 equivalents of at least one diol having 2 to 18 carbon
atoms to
form an isocyanate functional urethane prepolymer;
(b) reacting the isocyanate functional urethane prepolymer with about 0.05
to about 0.9 equivalents of at least one branched polyol having 4 to 18 carbon
atoms
and at least 3 hydroxyl groups and up to about 0.45 equivalents of at least
one diol
having 2 to 18 carbon atoms, wherein the reaction product components are
essentially
free of polyester polyol and polyether polyol.
[00335] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group C comprising the step of reacting
in a
one pot process components comprising: at least one polyisocyanate trimer or
branched polyisocyanate, the polyisocyanate having at least three isocyanate
functional groups; and at least one aliphatic polyol having 4 to 18 carbon
atoms and at
least two hydroxyl groups, wherein the reaction product components are
essentially
free of polyester polyol and polyether polyol.
[00336] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group D comprising the step of reacting
in a
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CA 02647153 2012-12-19
one pot process components comprising: at least one polyisocyanate; at least
one
branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups;
and at
least one polyol having one or more bromine atoms, one or more phosphorus
atoms or
combinations thereof.
[00337] In other non-limiting embodiments, the present invention provides
method of preparing polyurethanes of Group D comprising the steps of: reacting
at
least one polyisocyanate and at least one branched polyol having 4 to 18
carbon
atoms and at least 3 hydroxyl groups to form a polyurethane prepolymer; and
reacting
the polyurethane prepolymer with at least one polyol having one or more
bromine
atoms, one or more phosphorus atoms or combinations thereof to form the
polyurethane. In some non-limiting embodiments, about 0.1 to about 0.15
equivalents
of the branched polyol are reacted with about 1 equivalent of polyisocyanate
in step (a)
and step (b) further comprises reacting the polyurethane prepolymer with the
polyol
and about 0.15 to about 0.9 equivalents of the branched polyol to form the
polyurethane.
[00338] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group E comprising the step of reacting
in a
one pot process components comprising: about 1 equivalent of at least one
polyisocyanate; about 0.3 to about 1 equivalents of at least one branched
polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and about 0.01 to
about
0.3 equivalents of at least one polycarbonate diol, wherein the reaction
product
components are essentially free of polyether polyol and amine curing agent.
[00339] In other non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group E comprising the steps of:
reacting at
least one polyisocyanate and at least one branched polyol having 4 to 18
carbon
atoms and at least 3 hydroxyl groups to form a polyurethane prepolymer; and
reacting
the polyurethane prepolymer with at least one polycarbonate diol to form the
polyurethane.
[00340] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group F comprising the step of reacting
in a
one pot process components comprising: (a) about 1 equivalent of at least one
polyisocyanate; (b) about 0.3 to about 1 equivalents of at least one branched
polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; (c) about 0.01 to
about
0.3 equivalents of at least one polycarbonate diol; and (d) about 0.1 to about
0.9
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CA 02647153 2012-12-19
equivalents of at least one diol having 2 to 18 carbon atoms, wherein the
reaction
product components are essentially free of polyether polyol.
[00341] In other non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group F comprising the steps of:(a)
reacting at
least one polyisocyanate and at least one branched polyol having 4 to 18
carbon
atoms and at least 3 hydroxyl groups to form a polyurethane prepolymer; and
(b)
reacting the polyurethane prepolymer with at least one polycarbonate diol and
at least
one diol having 2 to 18 carbon atoms to form the polyurethane, wherein the
reaction
product components are essentially free of polyether polyol.
[00342] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group G comprising the step of reacting
in a
one pot process components comprising: about 1 equivalent of at least one
polyisocyanate; about 0.3 to about 1 equivalents of at least one branched
polyol
having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and about 0.01 to
about
0.3 equivalents of at least one polyol selected from the group consisting of
polyester
polyol, polycaprolactone polyol and mixtures thereof; and about 0.1 to about
0.7
equivalents of at least one aliphatic diol, wherein the reaction product
components are
essentially free of polyether polyol and amine curing agent.
[00343] In other non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group G comprising the steps of:
reacting at
least one polyisocyanate and at least one branched polyol having 4 to 18
carbon
atoms and at least 3 hydroxyl groups to form a polyurethane prepolymer; and
reacting
the polyurethane prepolymer with at least one polyol selected from the group
consisting of polyester polyol, polycaprolactone polyol and mixtures thereof
and about
0.1 to about 0.7 equivalents of at least one aliphatic diol to form the
polyurethane.
[00344] In some non-limiting embodiments, the present invention provides
methods of preparing polyurethanes of Group H comprising the steps of:
reacting
components comprising: at least one polyisocyanate; at least one
polycaprolactone
polyol; and at least one polyol selected from the group consisting of
polyalkylene
polyol, polyether polyol and mixtures thereof, to form a polyurethane
prepolymer; and
reacting the prepolymer with at least one diol having 2 to 18 carbon atoms to
form the
polyurethane.
Polv(ureaurethanes)
- 79 -
CA 02647153 2012-12-19
[00345]
Poly(ureaurethane)s can be prepared from any of the above
polyurethanes of Groups A-H by including one or more amine curing agents in
the
reaction components. The amine functionality of the amine curing agent can
react with
isocyanate groups to form urea linkages or units within the polyurethane
matrix.
Suitable amounts of amine curing agents and reaction conditions are discussed
in
detail above.
Poly(ureaurethane) Synthesis A
[00346] Alternatively
or additionally, urea linkages or units can be formed within
the polyurethane matrix to the extent desired by reacting isocyanate
functional groups
of the polyisocyanate with water. As shown in Step 1 of the reaction scheme of
Poly(ureaurethane) Synthesis A below, isocyanate functional groups are
converted to
carbamate functional groups by the reaction with water. In some non-
limiting
embodiments, the equivalent ratio of NCO:water ranges from about 10:1 to about
2:1,
or about 5:1 to about 2:1, or about 3:1 to about 2:1.
[00347] The isocyanate
shown in Step 1 is a diisocyanate in which R is any
linking group, such as aliphatic, cycloaliphatic, aromatic, heterocycle, etc.
as described
in detail above. However, one skilled in the art would understand that the
isocyanate
can have one or more, two or more, three or more or a higher number of
isocyanate
functional groups, as desired. Examples of suitable isocyanates can be any of
the
isocyanates discussed above. In some non-limiting embodiments, the
polyisocyanate
is one or more aliphatic polyisocyanates. In some non-limiting embodiments,
the
polyisocyanate is 4,4'-methylene-bis-(cyclohexyl isocyanate) (such as
DESMODURTNA
W).
[00348] Removal of
carbon dioxide facilitates conversion of the carbamate
groups into amine groups. Excess isocyanate is desirable to ensure essentially
complete consumption of the water. Also, it is desirable to remove essentially
all of the
carbon dioxide generated to facilitate conversion to amine groups. The water
can be
reacted with the polyisocyanate or polyurethane polyisocyanate prepolymer at a
temperature of up to about 60 C under vacuum. The vacuum pressure should be
low
enough so as not to remove water from the system, and can range for example
from
about 10 to about 20 mm Hg (about 1333 to about 2666 Pa) for a time period of
about
to about 30 minutes. After the reaction is essentially complete, i.e., no
further
carbon dioxide is formed, the temperature can be increased to at least about
100 C or
about 110 C and heated for about 2 to about 24 hours, or about 2 hours, using
10 ppm
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CA 02647153 2012-12-19
or more of catalyst such as dibutyltin diacetate. After substantially all of
the water
reacts with the excess isocyanate, the amine that is formed reacts essentially
instantaneously with the isocyanate.
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CA 02647153 2012-12-19
Poly(ureaurethane) Synthesis A
Step 1 0=C--=-N¨R¨N=C=0 +
(excess)
+
H20
catalyst
0 0
II H H II
HO¨C¨N¨R¨N¨C¨OH + 0=C=N¨R¨N=C=0
Ilr
t CO2 + H2N¨R¨NH2
Step 2
H2N¨R¨NH2 + 0=-C=--N¨R¨N=C=0
(excess)
Ir
0 0
H II H H II H
0=C=N¨R¨N¨C¨N¨R¨N¨C¨N¨R¨N=--C=0
Step 3
0 0
H II H H II H
0=C=N¨R¨N¨C¨N¨R¨N¨C¨N¨R¨N=C=O
+
R1¨(OH),
0 0 0 0
IR1-0-1j-111¨R F1\1¨ Id¨r1 R rl¨Id¨rl¨R¨EN¨Id-0¨
x
_
- 82 -
CA 02647153 2012-12-19
[00349] As is well known to those skilled in the art, certain amine curing
agents
(such as aliphatic amine curing agents having 2 to 18 carbon atoms, e.g.,
ethylene
diamine, diethylenediamine, diaminobutane, PACM, diamine hexane, 1,10-
decanediamine) are highly reactive and impractical to use under normal
production
conditions because the amine functionality begins to react with oxygen present
in the
ambient air very quickly to discolor the polymerizate. Aliphatic amine curing
agents
are typically very hygroscopic and difficult to keep dry. Generally, aliphatic
amines are
so reactive as to be impractical for making 100% solids, transparent, low
color and low
haze plastics.
[00350] By forming the amine in situ as discussed above and shown in Step
2,
amines can be generated in situ that normally are not practical to use under
normal
production conditions without formation of undesirable side products, color or
haze.
Also, the rate of reaction can be more easily regulated. This reaction can be
used for
any type of polyisocyanate described above, but is especially useful for
converting
aliphatic polyisocyanates to amines as described above.
[00351] As shown in Step 2 above, the amine formed in situ reacts with
another
isocyanate to form a urea group. Use of excess polyisocyanate permits
formation of
an isocyanate functional urea prepolymer. In some non-limiting embodiments,
the
equivalent ratio of NCO:amine functional groups ranges from about 1:0.05 to
about
1:0.7, or about 1:0.05 to about 1:0.5, or about 1:0.05 to about 1:0.3.
Suitable reaction
temperatures can range from about 25 C to about 60 C with a catalyst such as a
tin
catalyst. After the water is reacted and the carbon dioxide removed, the
reaction
temperature can be increased up to about 90 C for about 2 to about 4 hours.
Alternatively, the reaction can proceed at about 25 C for up to about 8 hours
until
complete. Optionally, one or more polyols or diols as described above can be
included
in this reaction to form isocyanate functional urethane prepolymers, as shown
in
Poly(ureaurethane) Synthesis B, described in further detail below.
[00352] As shown in Step 3 of the reaction scheme of Poly(ureaurethane)
Synthesis A above, the polyol and/or diol can be reacted with the isocyanate
functional
urea prepolymer(s) to form poly(ureaurethane)s of the present invention. The
polyol
shown in Step 3 can be a diol (m=2), triol (m=3) or higher hydroxyl functional
material
(m=4 or more) as described above in which R is any linking group, such as
aliphatic,
cycloaliphatic, aromatic, heterocycle, etc. as described in detail above with
respect to
the polyols. Examples of suitable polyols can be any of the polyos discussed
above.
In some non-limiting embodiments, the polyol can be trimethylolpropane and
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CA 02647153 2012-12-19
butanediol and/or pentanediol. Suitable amounts of polyols for reacting with
the
isocyanate functional urea prepolymer as polyisocyanate are discussed in
detail
above. In the above poly(ureaurethane), x can range from 1 to about 100, or
about 1
to about 20.
[00353] In some non-limiting embodiments, to form the poly(ureaurethane)
the
isocyanate functional prepolymer is heated to a temperature of about 90 C, the
polyol(s) are added and heated to about 90 C. The temperature can be increased
to
about 100 C or about 110 C to facilitate compatibilization, then about 2 to
about 4_mm
of vacuum can be applied for about 3 to about 5 minutes.
[00354] To prepare an article, for example, the mixture can be poured or
pressure cast into a release-coated glass casting mold to form an article of
desired
thickness and dimensions. In some embodiments, the casting mold is preheated
to a
temperature of about 200 F (93.3 C). The filled mold or cell can be placed in
an oven
at a temperature of about 250 F (121 C) to about 320 F (160 C) and cured for
about
24 to about 48 hours, for example. The cell can be removed from the oven and
cooled
to a temperature of about 25 C and the cured polymer released from the casting
mold.
Group I
[00355] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s of Group I comprising a reaction product of components
comprising: (a) at least one isocyanate functional urea prepolymer comprising
a
reaction product of: (1) at least one polyisocyanate; and (2) water; and (b)
at least one
branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups,
wherein
the reaction product components are essentially free or free of amine curing
agents.
Suitable polyisocyanates and branched polyol(s) having 4 to 18 carbon atoms
are
described in detail above. If present, the amine curing agent(s) can be
present in an
amount as defined above as essentially free. Any of the other optional
polyols,
catalysts or other additives described above can be included as reaction
components
in amounts as described above with respect to the foregoing Groups A-H.
[00356] In some non-limiting embodiments, the present invention provides
methods of preparing poly(ureaurethane)s of Group I comprising the steps of:
(a)
reacting at least one polyisocyanate and water to form an isocyanate
functional urea
prepolymer; and (b) reacting reaction product components comprising the
isocyanate
functional urea prepolymer with at least one branched polyol having 4 to 18
carbon
atoms and at least 3 hydroxyl groups, wherein the reaction product components
are
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CA 02647153 2012-12-19
essentially free of amine curing agent. The reaction synthesis can be as
described
above with respect to Poly(ureaurethane) Synthesis A. Optionally, a portion of
one or
more polyols or diols as described above can be included in this reaction to
form
isocyanate functional urethane prepolymer which is then further reacted with
another
portion of polyol and/or diol, as shown in Poly(ureaurethane) Synthesis B,
described in
further detail below.
Group J
[00357] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s of Group J comprising a reaction product of components
comprising: (a) at least one isocyanate functional urea prepolymer comprising
a
reaction product of: (1) at least one polyisocyanate selected from the group
consisting
of polyisocyanate trimers and branched polyisocyanates, the polyisocyanate
having at
least three isocyanate functional groups; and (2) water; and (b) at least one
aliphatic
polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups.
[00358] Examples of suitable polyisocyanate trimers and branched
polyisocyanates and polyol(s) are discussed above. Any of the other optional
polyols,
amine curing agent, catalysts or other additives described above can be
included as
reaction components in amounts as described above with respect to the
foregoing
Groups A-H. In some non-limiting embodiments, the reaction components are
essentially free or free of amine curing agents as described above.
[00359] In other non-limiting embodiments, the present invention provides
methods of preparing poly(ureaurethane) comprising the steps of: (a) reacting
at least
one polyisocyanate selected from the group consisting of polyisocyanate
trimers and
branched polyisocyanates and water to form an isocyanate functional urea
prepolymer; and (b) reacting reaction product components comprising the
isocyanate
functional urea prepolymer with at least one aliphatic polyol having 4 to 18
carbon
atoms and at least 2 hydroxyl groups, wherein the reaction product components
are
essentially free of amine curing agent.
[00360] The reaction synthesis can be as described above with respect to
Poly(ureaurethane) Synthesis A. Optionally, a portion of one or more polyols
or diols
as described above can be included in this reaction to form isocyanate
functional
urethane prepolymer which is then further reacted with another portion of
polyol and/or
diol, as shown in Poly(ureaurethane) Synthesis B, described in further detail
below.
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CA 02647153 2012-12-19
Poly(ureaurethane) Synthesis B
[00361] As shown
generally in Poly(ureaurethane) Synthesis B below, in other
non-limiting embodiments urea linkages or units can be formed within the
polyurethane
matrix to the extent desired by reacting polyisocyanate(s) and a portion of
the polyol(s)
to form at least one isocyanate functional urethane prepolymer, and then
reacting the
isocyanate functional urethane prepolymer(s) with water. As shown in Step 1 of
the
reaction scheme of Poly(ureaurethane) Synthesis B below, a portion of the
polyol(s)
and/or diol(s) can be reacted with polyisocyanate(s) to form the at least one
isocyanate functional urethane prepolymer. In some non-limiting embodiments,
the
equivalent ratio of NCO:OH functional groups ranges from about 1:0.05 to about
1:0.7,
or about 1:0.05 to about 1:0.5, or about 1:0.05 to about 1:0.3. It is
desirable to use
excess isocyanate to ensure essentially complete conversion of the hydroxyl
groups to
urethane groups.
[00362] The isocyanate
shown in Step 1 is a diisocyanate in which R is any
linking group, such as aliphatic, cycloaliphatic, aromatic, heterocycle, etc.
as described
in detail above. However, one skilled in the art would understand that the
isocyanate
can have one or more, two or more, three or more or a higher number of
isocyanate
functional groups, as desired. Examples of suitable isocyanates can be any of
the
polyisocyanates discussed above. In some non-
limiting embodiments, the
polyisocyanate is one or more aliphatic polyisocyanates. In some non-
limiting
embodiments, the polyisocyanate is 4,4'-methylene-bis-(cyclohexyl isocyanate)
(such
as DESMODURTm VV).
[00363] The polyol
shown in Step 1 can be a diol (m=2), triol (m=3) or higher
hydroxyl functional material (m= 4 or more) as described above in which R is
any
linking group, such as aliphatic, cycloaliphatic, aromatic, heterocycle, etc.
as described
in detail above with respect to the polyols. Examples of suitable polyols can
be any of
the polyols discussed above. In some non-limiting embodiments, the polyol can
be
trimethylolpropane and butanediol and/or pentanediol. Optionally, one or more
catalysts such as are described above can be used to facilitate the reaction.
The
polyisocyanate can be reacted with the polyol to form the isocyanate
functional
urethane prepolymer by charging the reactants into a kettle and adding about
10 ppm
or more of catalyst, such as a tin, bismuth or zirconium catalyst. The mixture
can be
heated to a temperature of about 100 C or about 110 C for about 2 to about 4
hours
until all of the hydroxyl functionality is reacted. FTIR spectroscopy can be
used to
determine the extent of reaction.
- 86 -
CA 02647153 2012-12-19
1003641 Urea linkages or units can be formed within the polyurethane matrix
to
the extent desired by reacting isocyanate functional groups of the isocyanate
functional urethane prepolymer with water. As shown in Step 2 of the reaction
scheme
of Poly(ureaurethane) Synthesis B below, isocyanate functional groups are
converted
to carbamate functional groups by the reaction with water. In some non-
limiting
embodiments, the equivalent ratio of NCO: water ranges from about 1:0.05 to
about
1:0.7, or about 1:0.05 to about 1:0.5, or about 1:0.05 to about 1:0.3.
1003651 Removal of carbon dioxide facilitates conversion of the carbamate
groups into amine groups. Excess isocyanate is desirable to ensure essentially
complete consumption of the water. Also, it is desirable to remove essentially
all of the
carbon dioxide generated to facilitate conversion to amine groups. To prevent
the
removal of water under vacuum, the reaction can be started at a temperature of
about
25 C, then raised to a temperature of about 60 C while applying vacuum to
remove
the carbon dioxide. After cessation of carbon dioxide formation, the reaction
temperature can be increased to about 100 C or about 110 C for about 2 to
about 4
hours.
1003661 As discussed above, certain amine curing agents (such as aliphatic
amine curing agents) are highly reactive and impractical to use under normal
production conditions. By forming the amine in situ as discussed above and
shown in
Step 2, amines can be generated in situ that normally are not practical to use
under
normal production conditions without formation of undesirable side products.
Also, the
rate of reaction can be more easily regulated. This reaction can be used for
any type
of polyisocyanate described above, but is especially useful for converting
aliphatic
polyisocyanates to amines as described above.
1003671 As shown in Step 3 below, the amine formed in situ reacts with
another
isocyanate to form a urea group. Use of excess polyisocyanate permits
formation of
an isocyanate functional ureaurethane prepolymer. The isocyanate functional
ureaurethane prepolymer can be prepared by reacting a stoichiometric excess of
the
polyisocyanate with the amine under substantially anhydrous conditions at a
temperature ranging from about 25 C and about 150 C or about 110 C until the
reaction between the isocyanate groups and the amine groups is substantially
complete. The polyisocyanate and amine components are suitably reacted in such
proportions that the ratio of number of isocyanate groups to the number of
amine
groups is in the range of about 1:0.05 to about 1:0.7, or within the range of
about
1:0.05 to 1:0.3.
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CA 02647153 2012-12-19
[00368] As shown in Step 4 of the reaction scheme of Poly(ureaurethane)
Synthesis B below, the isocyanate functional ureaurethane prepolymer can be
reacted
with another portion of polyol and/or diol to form the poly(ureaurethane)s of
the present
invention. The polyol shown in Step 4 can be a diol, triol or higher hydroxyl
functional
material as described above in which R is any linking group, such as
aliphatic,
cycloaliphatic, aromatic, heterocycle, etc. as described in detail above with
respect to
the polyols. Examples of suitable polyols can be any of the polyols discussed
above.
In some non-limiting embodiments, the polyol can be trimethylolpropane and
butanediol and/or pentanediol. Suitable amounts of polyols for reacting with
the
isocyanate functional ureaurethane prepolymer as polyisocyanate are discussed
in
detail above.
[00369] The isocyanate functional ureaurethane prepolymer can be reacted
with
the other portion of polyol and/or diol (n= 2 or more) under substantially
anhydrous
conditions at a temperature ranging from about 120 C to about 160 C until the
reaction between the isocyanate groups and the hydroxyl groups is
substantially
complete. The isocyanate functional ureaurethane prepolymer and polyol(s)
and/or
diol(s) components are suitably reacted in such proportions that the ratio of
number of
isocyanate groups to the number of hydroxyl groups is in the range of about
1.05:1 to
about 1:1 In the poly(ureaurethane) of Group K, y can range from 1 to about
500 or
higher, or about 1 to about 200.
[00370] The cure temperature depends upon the glass transition temperature
of
the final polymer. In some embodiments, for complete cure the cure temperature
should be greater than the glass transition temperature. For example, the cure
temperature can range from about 140 C to about 180 C or about 143 C to about
180 C.
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CA 02647153 2012-12-19
Roly(ureaurethane) Synthesis B
Step 1 0=C=N¨R¨N=C=O
(excess)
+
R1¨(OH),
lir catalyst
4 0
Ri 0õ--IN-R-N=C=0 + 0=C--=N¨R¨N=¨C-=0
m
Step 2
0
II +
Ri4 0¨C¨NH ¨R¨N7---.C=0 (excess)
m +H20
Il
4 0 0
Ri 0_1J-1-N1-R ¨1-N-1¨il¨OH + 0-=--
C=N¨R¨N---=-C=0
m
li
0
t CO2 + R1 4 0¨ ij--11¨R ¨NH2
m
- 89 -
CA 02647153 2012-12-19
Step 3
R10¨C¨N¨R¨NH24 0
II ti, + 0=C=N¨R¨N=C=0
m (excess)
4 0
0
II
R1 0.__IJ-,,-õ-R-FIVI-C-FIV-R-N-C m
Step 4
4 0
0
II
R1 0J¨FNI¨R¨IR1¨C¨rl¨R¨N C 0
m
+
R2¨(01-1)n
Ilr
0
[ 0
0
R1 0¨ ij 1-N1 R¨N1-11¨F1\11¨R¨k1-11-0¨R2
Y
- 90 -
CA 02647153 2012-12-19
Group K
[00371] In some non-limiting embodiments, the present invention provides
poly(ureaurethane)s of Group K comprising a reaction product of components
comprising: (a) at least one isocyanate functional ureaurethane prepolymer
comprising
the reaction product of: (1) at least one isocyanate functional urethane
prepolymer
comprising the reaction product of: (i) a first amount of at least one
polyisocyanate;
and (ii) a first amount of at least one branched polyol; and (2) water, to
form an
isocyanate functional ureaurethane prepolymer; and (b) a second amount of at
least
one polyisocyanate and a second amount of at least one branched polyol.
[00372] Examples of suitable polyisocyanates and polyol(s) are discussed
above. Any of the other optional polyols, amine curing agents, catalysts or
other
additives described above can be included as reaction components in amounts as
described above with respect to the foregoing Groups A-G. In some non-limiting
embodiments, the reaction components are essentially free or free of amine
curing
agent as described above or free of amine curing agent.
[00373] In other non-limiting embodiments, the present invention provides
methods of preparing poly(ureaurethane)s of Group K comprising the steps of:
(a)
reacting at least one polyisocyanate and at least one branched polyol having 4
to 18
carbon atoms and at least 3 hydroxyl groups to form an isocyanate functional
urethane
prepolymer; (b) reacting the isocyanate functional urethane prepolymer with
water and
polyisocyanate to form an isocyanate functional ureaurethane prepolymer; and
(c)
reacting reaction product components comprising the isocyanate functional
ureaurethane prepolymer with at least one aliphatic polyol having 4 to 18
carbon
atoms and at least 2 hydroxyl groups, wherein the reaction product components
are
essentially free of amine curing agent. The reaction synthesis can be as
described
above with respect to Poly(ureaurethane) Synthesis B.
Group L
[00374] In other non-limiting embodiments, the present invention provides
poly(ureaurethane)s of Group L comprising a reaction product of components
comprising: (a) at least one isocyanate functional ureaurethane prepolymer
comprising
the reaction product of: (a) (1) at least one isocyanate functional urethane
prepolymer
comprising the reaction product of: (i) a first amount of at least one
polyisocyanate
selected from the group consisting of polyisocyanate trimers and branched
- 91 -
CA 02647153 2012-12-19
polyisocyanates, the polyisocyanate having at least three isocyanate
functional
groups; and (ii) a first amount of at least one aliphatic polyol; and (2)
water, to form an
isocyanate functional ureaurethane prepolymer; and (b) a second amount of at
least
one polyisocyanate and a second amount of at least one aliphatic polyol.
[00375] Examples of suitable polyisocyanate trimers and branched
polyisocyanates having at least three isocyanate functional groups and
polyol(s) are
discussed above. Any of the other optional polyols, amine curing agent,
catalysts or
other additives described above can be included as reaction components in
amounts
as described above with respect to the foregoing Groups A-G. In some non-
limiting
embodiments, the reaction components are essentially free or free of amine
curing
agent as described above.
[00376] In other non-limiting embodiments, the present invention provides
methods of preparing poly(ureaurethane)s of Group L comprising the steps of:
(a)
reacting at least one polyisocyanate selected from the group consisting of
polyisocyanate trimers and branched polyisocyanates and at least one aliphatic
polyol
having 4 to 18 carbon atoms and at least 2 hydroxyl groups to form an
isocyanate
functional urethane prepolymer; (b) reacting the isocyanate functional
urethane
prepolymer with water and polyisocyanate to form an isocyanate functional
ureaurethane prepolymer; and (c) reacting reaction product components
comprising
the isocyanate functional ureaurethane prepolymer with at least one aliphatic
polyol
having 4 to 18 carbon atoms and at least 2 hydroxyl groups, wherein the
reaction
product components are essentially free or free of amine curing agent. The
reaction
synthesis can be as described above with respect to Poly(ureaurethane)
Synthesis B.
[00377] As discussed above, poly(ureaurethane)s can be prepared by
including
one or more amine curing agents in the reaction components. The amine
functionality
of the amine curing agent can react with isocyanate groups to form urea
linkages or
units within the polyurethane matrix.
Group M
[00378] In other non-limiting embodiments, the present invention provides
poly(ureaurethane)s of Group M comprising a reaction product of components
comprising: about 1 equivalent of at least one polyisocyanate; about 0.1 to
about 0.9
equivalents of at least one branched polyol having 4 to 18 carbon atoms and at
least 3
hydroxyl groups; about 0.1 to about 0.9 equivalents of at least one aliphatic
diol having
2 to 18 carbon atoms; and at least one amine curing agent, wherein the
reaction
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CA 02647153 2012-12-19
product components are essentially free or free of polyester polyol and
polyether
polyol.
[00379] Non-limiting examples of suitable polyisocyanates, branched polyols
having 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols
and amine
curing agents for use as reaction components for preparing the polyurethanes
of
Group M are discussed in detail above with respect to Group A.
[00380] In some non-limiting embodiments, the amount of branched polyol
used
to form the polyurethane of Group M can be about 0.3 to about 0.98
equivalents, in
other non-limiting embodiments about 0.5 to about 0.98 equivalents, and in
other non-
limiting embodiments about 0.3 equivalents or about 0.9 or about 0.98
equivalents.
[00381] In some non-limiting embodiments, the amount of aliphatic diols
used to
form the polyurethane of Group M can be about 0.1 to about 0.7 equivalents, in
other
non-limiting embodiments about 0.1 to about 0.5 equivalents, and in other non-
limiting
embodiments about 0.3 equivalents.
[00382] In some non-limiting embodiments, the amount of amine curing agent
used to form the polyurethane of Group M can be about 0.1 to about 0.9
equivalents,
in other non-limiting embodiments about 0.1 to about 0.7 equivalents, and in
other
non-limiting embodiments about 0.3 equivalents.
[00383] With respect to poly(ureaurethane)s of Group M, essentially free of
polyester polyol and polyether polyol means that the polyester polyol and
polyether
polyol can be present as reaction components in respective amounts as
described for
the polyurethane of Group A above, or the reaction components can be free of
one or
both of polyester polyol and polyether polyol.
[00384] Any of the other optional polyols, catalysts or other additives
described
above can be included as reaction components in amounts as described above
with
respect to the foregoing Groups A-H.
[00385] In other non-limiting embodiments, the present invention provides
methods of preparing poly(ureaurethane) comprising the step of reacting in a
one pot
process components comprising: at least one polyisocyanate; at least one
branched
polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; at least
one
aliphatic diol having 2 to 18 carbon atoms; and amine curing agent, wherein
the
reaction product components are essentially free or free of polyester polyol
and
polyether polyol.
Group N
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CA 02647153 2012-12-19
[00386] In other non-limiting embodiments, the present invention provides
poly(ureaurethane)s of Group N comprising a reaction product of components
comprising: (a) at least one polyisocyanate selected from the group consisting
of
polyisocyanate trimers and branched polyisocyanates, the polyisocyanate having
at
least three isocyanate functional groups; (b) about 0.1 to about 0.9
equivalents of at
least one polyol having 4 to 18 carbon atoms and at least 2 hydroxyl groups;
and (c) at
least one amine curing agent, wherein the reaction product components are
essentially
free or free of polyester polyol and polyether polyol.
[00387] Non-limiting examples of suitable polyisocyanates, branched polyols
having 4 to 18 carbon atoms and at least 3 hydroxyl groups, aliphatic diols
and amine
curing agents for use as reaction components for preparing the polyurethanes
of
Group N are discussed in detail above with respect to Groups A -C.
[00388] In some non-limiting embodiments, the amount of branched polyol
used
to form the polyurethane of Group N can be about 0.3 to about 0.98
equivalents, in
other non-limiting embodiments about 0.5 to about 0.98 equivalents, and in
other non-
limiting embodiments about 0.3 equivalents or about 0.9 or about 0.98
equivalents.
[00389] In some non-limiting embodiments, the amount of aliphatic diols
used to
form the polyurethane of Group N can be about 0.1 to about 0.7 equivalents, in
other
non-limiting embodiments about 0.1 to about 0.5 equivalents, and in other non-
limiting
embodiments about 0.3 equivalents.
[00390] In some non-limiting embodiments, the amount of amine curing agent
used to form the polyurethane of Group N can be about 0.1 to about 0.7
equivalents, in
other non-limiting embodiments about 0.1 to about 0.5 equivalents, and in
other non-
limiting embodiments about 0.3 equivalents.
[00391] With respect to poly(ureaurethane)s of Group N, essentially free of
polyester polyol and polyether polyol means that the polyester polyol and
polyether
polyol can be present as reaction components in respective amounts as
described for
the polyurethane of Group A above, or the reaction components can be free of
one or
both of polyester polyol and polyether polyol.
[00392] Any of the other optional polyols, catalysts or other additives
described
above can be included as reaction components in amounts as described above
with
respect to the foregoing Groups A-H.
[00393] In other non-limiting embodiments, the present invention provides
methods of preparing poly(ureaurethane) comprising the step of reacting in a
one pot
process components comprising: at least one polyisocyanate selected from the
group
- 94 -
CA 02647153 2012-12-19
consisting of polyisocyanate trimers and branched polyisocyanates; at least
one
aliphatic polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups;
at least
one aliphatic diol having 2 to 18 carbon atoms; and amine curing agent,
wherein the
reaction product components are essentially free or free of polyester polyol
and
polyether polyol.
[00394] In some
embodiments, the poly(ureaurethanes) of Groups I¨N of the
present invention can be thermosetting.
Group 0
[00395] In some non-
limiting embodiments, the present invention provides
polyurethane materials comprising a first portion of crystalline particles
having self-
orientation and bonded together to fix their orientation along a first
crystallographic
direction and a second portion of crystalline particles having self-
orientation and
bonded together to fix their orientation along a second crystallographic
direction, the
first crystallographic direction being different from the second
crystallographic
direction, wherein said crystalline particles comprise at least about 30% of
the total
volume of the polyurethane material.
[00396] The particles
interact with one another or with a substrate surface to
align their crystallographic axes in one, two or three dimensions. As used
herein,
"align" or "aligned" with respect to the crystalline particles means that the
particles of
that crystalline portion are arranged in an array of generally fixed position
and
orientation. The preferred degree of alignment will depend on the intended
application
for the material. For purposes of alignment, it is desirable that the
particles have
uniform shapes with dominant planar surfaces in a suitable orientation, such
as
perpendicular to or parallel to, with respect to the desired direction of
alignment.
[00397] In some non-
limiting embodiments, the first portion of the crystalline
particles is aligned in two dimensions. In some non-limiting embodiments, the
first
portion of the crystalline particles is aligned in three dimensions. In
some
embodiments, the crystalline particles are aligned along a distance ranging
from about
1 nm to about 50 nm along any direction.
[00398] In some non-
limiting embodiments, the second portion of the crystalline
particles is aligned in two dimensions. In some non-limiting embodiments, the
second
portion of the crystalline particles is aligned in three dimensions.
[00399] The
crystalline particles of the present invention have at least "Self-
Aligning" morphologies. As used herein, "Self-Aligning" morphologies include
any
- 95 -
CA 02647153 2012-12-19
particles that are capable of self-organizing to form a polycrystalline
structure wherein
the single particles are aligned along at least one crystallographic direction
into areas
of higher density and order, for example like lamellae. Examples of crystal
particle
morphologies with Self-Aligning morphologies include cubic particles,
hexagonal
platelets, hexagonal fibers, rectangular platelets, rectangular particles,
triangular
platelets, square platelets, tetrahedral, cube, octahedron and mixtures
thereof.
[00400] Self-Aligning morphologies may establish an orientation that could
be
up to about 10 degrees from the desired alignment direction, yet still
sufficiently
capture the desired properties. Thus, particles having such morphologies
include
particles that essentially have the desired morphology. For instance, for
particles that
are cubes, the particles need not be perfect cubes. The axes need not be at
perfect
90 degree angles, nor exactly equal in length. Corners may also be cut off of
the
particles. Furthermore, "cube" or "cubic" is intended to refer to morphology,
and is not
intended to limit the particles to cubic crystal systems. Instead, single
crystal particles
that have orthorhombic, tetragonal or rhombohedral crystal structure may also
be
employed as cubes if they possess the defined cubic morphology. In other
words, any
essentially orthogonal single crystal particles in which the faces are
essentially square,
essentially rectangular, or both, that possess an essentially cubic morphology
are
considered cubes for purposes of the present invention.
[00401] The crystalline particles can be aligned in monolithic structures
consisting of a single layer of crystals or multiple layers of crystals. The
layer or layers
are generally planar, although the layers can conform to curved surfaces or
complex
geometries depending on the shape of the supporting substrate material during
formation and curing of the polyurethane.
[00402] The polycrystalline materials of the present invention are prepared
by
packing and aligning a plurality of single crystal particles into an aligned
array to
achieve one, two and three-dimensional alignment. In some non-limiting
embodiments, the particles can self-assemble into arrays upon aging or heat
treatment. In some non-limiting embodiments, to obtain a level of solid state
diffusion
sufficient to bind together adjacent particles, a temperature above about half
of the
melting temperature is required, which is most generally in the range of about
35 C to
about 100 C. The temperature range selected will depend upon the material
being
bonded, but can be readily determined by those of ordinary skill in the art
without
undue experimentation within the defined range. The preparation steps may be
repeated to form a polycrystalline material having multiple layers of aligned
particles.
- 96 -
CA 02647153 2012-12-19
The resulting material is essentially a three-dimensional object with one,
two, or three
dimensional alignment of single crystal particles within.
[00403] Fig. 4 is a
TEM photomicrograph showing a casting prepared from a
polyurethane according to Example A, Formulation 2. This casting was analyzed,
using TEM, two weeks after polymerization of the polyurethane. The casting had
been
stored at ambient temperature (about 25 C) for the two week period. As shown
in Fig.
4, no discernible regions of aligned crystals were observed.
[00404] Fig. 5 is a
TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2. This casting was analyzed, using TEM,
three
weeks after polymerization of the polyurethane. The casting had been stored at
ambient temperature (about 25 C) for the three week period. As shown in Fig.
5, initial
formation of crystalline domains is observed.
[00405] Fig. 6 is a
TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2. This casting was analyzed, using TEM,
seven
months after polymerization of the polyurethane. The casting had been stored
at
ambient temperature (about 25 C) for the seven month period. In the
photomicrograph Fig. 6, a region of aligned crystals generally parallel to the
arrows is
shown.
[00406] Fig. 7 is an
electron diffraction pattern of the polyurethane Example A,
Formulation 2 stored at ambient temperature (about 25 C) for seven months. The
bright spots in the pattern are reflections from the crystalline lattice
planes, which are
about 8 nanometers by about 4 nanometers in size.
[00407] Fig. 8 is a
TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2 prepared after aging at ambient
temperature
for about 7 months. In this photomicrograph Fig. 8, many regions or domains of
aligned crystals generally parallel to the arrows are shown, the domains being
oriented
in different directions and showing a higher density of domains than the
samples aged
for three weeks.
[00408] Fig. 9 is a
TEM photomicrograph showing a first portion of a casting of a
polyurethane according to Example A, Formulation 2 prepared after aging at
ambient
temperature for about two to four weeks. The casting had been stored at
ambient
temperature for the two to four week period. As shown in Fig. 9, no
discernible regions
of aligned crystals were observed.
[00409] Fig. 10 is a
TEM photomicrograph showing a second portion of the
casting of the polyurethane according to Example A, Formulation 2 shown in
Fig. 9.
- 97 -
CA 02647153 2012-12-19
As shown in the circled area in Fig. 10, initial formation of crystalline
domains is
observed.
[00410] The sample
shown in Figs. 9 and 10 had a Gardner Impact Strength of
180 in-lbs.
[00411] Fig. 11 is a
TEM photomicrograph showing a casting of a polyurethane
according to Example A, Formulation 2. This casting was analyzed, using TEM,
about
two to about four weeks after polymerization of the polyurethane. The casting
had
been stored at ambient temperature for the two to four week period. In the
photomicrograph Fig. 11, regions of aligned crystals in the circled areas are
shown.
[00412] Fig. 12 is a
TEM photomicrograph showing a first portion of a casting of
a polyurethane according to Example A, Formulation 2 prepared after aging at
ambient
temperature for about 7 months. In this photomicrograph Fig. 12, a large
region or
domain of aligned crystals is shown.
[00413] Fig. 13 is a
TEM photomicrograph showing a second portion of a
casting of a polyurethane according to Example A, Formulation 2 shown in Fig.
12. In
this photomicrograph Fig. 13, many regions or domains of aligned crystals are
shown,
the domains being oriented in different directions and showing a higher
density of
domains than the samples aged for a shorter period of time.
[00414] The sample
shown in Figs. 12 and 13 had a Gardner Impact Strength of
640 in-lbs.
[00415] Fig. 14 is a
graph of heat flow as a function of temperature measured
using Differential Scanning Calorimetry (DSC) for castings of a polyurethane
according
to Example A, Formulation 2 measured after aging at ambient conditions for two
weeks, three months and seven months, respectively. The melting endotherm
enthalpy of the crystalline domains increases with time, showing a change in
polymer
morphology and microstructure with time, even though the polymer is glassy and
highly crosslinked with a glass transition temperature of 235 F (113 C). As
the
number and size of the crystalline domains increases, the melting enthalpy
increases.
The Gardner Impact Strength increased over time. At two weeks, the Gardner
Impact
Strength was 180 in-lbs. At three months, the Gardner Impact Strength was 380
in-
lbs. At seven months, the Gardner Impact Strength was 640 in-lbs.
[00416] Fig. 15 is a
graph of Gardner Impact as a function of Young's Modulus
for castings of a polyurethane according to Example A, Formulations 2 and 1,
respectively, measured after aging at ambient conditions for seven months and
one
year, respectively. At seven months for Formulation 2, the Gardner Impact
Strength
- 98 -
CA 02647153 2012-12-19
was 640 in-lbs. At one year for Formulation 1, the Gardner Impact Strength was
400
in-lbs.
[00417] In some non-
limiting ,embodiments, the polyurethane material
comprises a monolithic agglomerate of the first portion of the crystalline
particles with
low-angle grain boundaries therebetween bonded together by a polymer phase.
[00418] In some non-
limiting embodiments, the polyurethane material
comprises a monolithic agglomerate of the second portion of the crystalline
particles
with low-angle grain boundaries therebetween bonded together by a polymer
phase.
[00419] In some non-
limiting embodiments, the polyurethane material
comprises a monolithic agglomerate of the first portion of the crystalline
particles with
low-angle grain boundaries and a generally amorphous phase therebetween.
[00420] In some non-
limiting embodiments, the polyurethane material
comprises a monolithic agglomerate of the second portion of the crystalline
particles
with low-angle grain boundaries and a generally amorphous phase therebetween.
[00421] In some non-
limiting embodiments, the thickness of the first portion of
crystalline particles is less than about 50 nanometers. In some non-
limiting
embodiments, the thickness of the second portion of crystalline particles is
less than
about 50 nanometers. The length and width, respectively, of the first portion
can vary,
for example about 4 nm by about 8 nm.
[00422] In some non-
limiting embodiments, the thickness of the first portion of
crystalline particles can range from about 10 nanometers to about 100
nanometers. In
some non-limiting embodiments, the thickness of the second portion of
crystalline
particles can range from about 4 nanometers to about 50 nanometers. The length
and
width, respectively, of the second portion can vary, for example about 4 nm by
about 8
nm.
[00423] In some non-
limiting embodiments, the crystalline particles comprise at
least about 30% of the total volume of the material. In other non-limiting
embodiments,
the crystalline particles comprise at least about 40%, or at least about 50%,
or at least
about 60%, or at least about 70%, or at least about 80%, or at least about 90%
of the
total volume of the material. The percentage of crystalline particles can be
determined
using DSC. For example, an article prepared from Formulation 2 as described
below,
aged at ambient conditions (about 25 C) for about 7 months had a crystallinity
of about
43% by volume.
[00424] In some non-
limiting embodiments, the polyurethane comprises a
reaction product of components consisting of: (a) about 1 equivalent of 4,4'-
methylene-
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bis-(cyclohexyl isocyanate); (b) about 0.3 equivalents of trimethylolpropane;
and (c)
about 0.7 equivalents of butanediol or pentanediol. In some non-
limiting
embodiments, the butanediol is 1,4-butanediol. In some non-limiting
embodiments, the
pentanediol is 1,5-pentanediol.
1004251 In some non-
limiting embodiments, the impact resistance of
polyurethanes and poly(ureaurethane)s of Groups A-M above according to the
present
invention can be improved by aging or heat treatment.
1004261 In some non-
limiting embodiments, the polyurethane material can be
aged for at least about 2 weeks after formation. In some non-limiting
embodiments,
the polyurethane material can be aged for at least about 2 months after
formation. In
some non-limiting embodiments, the polyurethane material has been aged for at
least
about 7 months after formation.
1004271 In some non-
limiting embodiments, the polyurethane material has been
heated to a temperature of about 90 C to about 150 C or about 200 F (about 93
C) to
about 290 F (about 143 C) for about 1 to about 24 hours after formation. In
some
non-limiting embodiments, the polyurethane is heated at a temperature
sufficient to
induce grain boundary mobility, so that the particles grow until impingement
of
adjacent crystal grain boundaries prevent further growth. The net result is a
polycrystalline microstructure, the grains of which for all practical purposes
are aligned
in two or three dimensions so that it performs like a single crystal with
respect to some
desired property.
[00428] Impact
resistance or flexibility can be measured using a variety of
conventional methods known to those skilled in the art. The flexibility of the
materials
can be measured by the Gardner Impact Test using a Gardner Variable Impact
Tester
in accordance with ASTM-D 5420-04, which consists of a 40-inch (101.6 cm)
aluminum tube in which an 8- or 16- lb (17.6- or 35.2- kg) weight is dropped
from
various heights onto a metal dart resting onto the substrate being tested (2
inch by 2
inch by 1/8 inch (5.1 cm by 5.1 cm by 0.3 cm) specimen size. In a non-limiting
embodiment, the impact strength results of the Gardner Impact Test of at least
about
65 in-lb (7.3 Joules) or from about 65 in-lb (7.3 Joules) to about 640 in-lb
(72 joules).
1004291 In another
embodiment, the impact resistance can be measured using
the Dynatup Test in accordance with ASTM-D 3763-02 can be conducted which
consists of a high velocity test with a load cell which measures total energy
absorption
in the first microseconds of the impact. The impact strength can be measured
in
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CA 02647153 2012-12-19
Joules. In a non-limiting embodiment, the substrate can have an impact
strength of at
least about 35 Joules or from about 35 to about 105 Joules.
Group P
[00430] In some non-limiting embodiments, the present invention provides
polyurethane powder coating compositions. The powder coating compositions can
be
prepared from any of the polyurethanes or poly(ureaurethane)s of Groups A-N
discussed in detail above.
[00431] In some non-limiting embodiments, the present invention provides
methods of preparing a polyurethane powder coating composition comprising the
steps of: reacting at least one polyisocyanate with at least one aliphatic
polyol to form
a generally solid, hydroxy functional prepolymer; melting the hydroxy
functional
prepolymer; melting at least one generally solid polyisocyanate to form a
melted
polyisocyanate; mixing the melted hydroxy functional prepolymer and melted
polyisocyanate to form a mixture; and solidifying the mixture to form a
generally solid
powder coating composition.
[00432] The generally solid, hydroxy functional prepolymer can be prepared
by
reacting the polyisocyanate(s) with excess aliphatic polyol(s) and catalyst in
amounts
as described above and heating the prepolymer to a temperature of about 140 C
or
about 150 C to about 180 C for about 1 to about 24 hours to facilitate
essentially
complete reaction of the components and formation of a generally solid
prepolymer.
[00433] In some non-limiting embodiments, the polyisocyanate is branched or
a
trimer as discussed above and the aliphatic polyol is an aliphatic diol having
from 4 to
18 carbon atoms, or 4 or 5 carbon atoms, such as propanediol, butanediol,
cyclohexane dimethanol, 1,10-decanediol and/or 1,12-dodecanediol. In other non-
limiting embodiments, the polyisocyanate can be any polyisocyanate as
discussed
above and the aliphatic polyol can be a branched diol having from 4 to 18
carbon
atoms, such as trimethylolpropane.
[00434] The equivalent ratio of isocyanate functional groups to hydroxyl
functional groups can range from about 1:0.9 to about 1:1.1, or about 1:1.
[00435] The generally solid polyisocyanate can be melted by, for example,
heating at a temperature of about 35 C to about 150 C for about 2 to about 24
hours
to form the melted polyisocyanate. The melted hydroxy functional prepolymer
and
melted polyisocyanate can be mixed and solidified to form a generally
homogeneous
mixture suitable for forming a powder coating, as discussed below. The
equivalent
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CA 02647153 2012-12-19
ratio of isocyanate functional groups of the polyisocyanate to hydroxyl
functional
groups of the hydroxy functional prepolymer can range from about 1.05:1 to
about
0.95:1, or about 1:1.
[00436] In other non-limiting embodiments, the present invention provides
methods of preparing a polyurethane powder coating composition comprising the
steps of: reacting at least one polyisocyanate with at least one aliphatic
polyol to form
a generally solid, hydroxy functional prepolymer; dissolving the hydroxy
functional
prepolymer in a first solvent to form a first solution; dissolving at least
one generally
solid polyisocyanate in a second solvent that is the same as or compatible
with the first
solvent to form a second solution; mixing the first and second solutions; and
removing
substantially all of the solvent to form a generally solid powder coating
composition.
[00437] In some non-limiting embodiments, the polyisocyanate(s) are
branched
or a trimer as discussed above and the aliphatic polyol is an aliphatic diol
having from
4 to 18 carbon atoms, or 4 or 5 carbon atoms, such as propanediol and/or
butanediol.
In other non-limiting embodiments, the polyisocyanate can be any
polyisocyanate as
discussed above and the aliphatic polyol can be a branched diol having from 4
to 18
carbon atoms, such as trimethylolpropane.
[00438] The generally solid, hydroxy functional prepolymer can be prepared
by
reacting the polyisocyanate(s) with excess aliphatic polyol(s) and catalyst in
types and
amounts as described above. The hydroxy functional prepolymer is dissolved in
a first
solvent to form a first solution. The solvent can be any solvent capable of
dissolving
the hydroxy functional prepolymer, such as a dipolar aprotic solvent, for
example m-
pyrole (N-methyl-2-pyrrolidone), N,N-dimethylformamide, N,N-dimethylacetamide,
dimethyl sulfoxide (DMSO), methylene chloride, dichlorobutane, cyclohexanone,
dimethyl formamide and/or acetonitrile solvent. The amount of solvent can
range from
about 20 to about 95 weight percent based upon weight of solids of the hydroxy
functional prepolymer.
[00439] The generally solid polyisocyanate in a second solvent that is the
same
as or compatible with the first solvent to form a second solution. The solvent
can be
any solvent capable of dissolving the generally solid polyisocyanate, such as
a dipolar
aprotic solvent, for example m-pyrole (N-methyl-2-pyrrolidone), N,N-
dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), methylene
chloride, dimethyl formamide and/or acetonitrile solvent. The amount of
solvent can
range from about 20 to about 95 weight percent based upon weight of the solids
of
polyisocyanate.
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[00440] The first and
second solutions are mixed and substantially all of the
solvent is removed, for example by vacuum in an oven, to form a generally
solid
powder suitable for use as a coating composition. The powder can
be milled or
micronized, if desired.
[00441] Curable powder
coating compositions useful in the present invention
are typically prepared by first dry blending the polymer, e.g., polyurethane
or
poly(ureaurethane) polymer, the crosslinking agent (if present), the particles
and
additives, such as degassing agents, flow control agents and catalysts, in a
blender,
e.g., a Henshel blade blender. The blender is operated for a period of time
sufficient to
result in a homogenous dry blend of the materials charged thereto. The
homogeneous
dry blend is then melt blended in an extruder, e.g., a twin screw co-rotating
extruder,
operated within a temperature range sufficient to melt but not gel the
components.
[00442] Optionally,
curable powder coating compositions of the present
invention may be melt blended in two or more steps. For example, a first melt
blend is
prepared in the absence of a cure catalyst. A second melt blend is prepared at
a lower
temperature, from a dry blend of the first melt blend and the cure catalyst.
The melt
blended curable powder coating composition is typically milled to an average
particle
size of from, for example, 15 to 30 microns.
[00443] Alternatively,
the powder coating compositions of the present invention
can be prepared by blending and extruding the ingredients as described above,
but
without the particles. The particles can be added as a post-additive to the
formulation
by simply mixing the particles into the milled powder coating composition,
such as by
mixing using a Henschel mixer. In some non-limiting embodiments, the powder
coating composition is slurried in a liquid medium, such as water, which may
be spray
applied.
Group Q
[00444] In some non-
limiting embodiments, the compositions of the present
invention can further comprise one or more types of reinforcing materials.
These
reinforcing materials can be present in any physical form desired, for example
as
particles, including but not limited to nanoparticles, agglomerates, fibers,
chopped
fibers, mats, etc.
[00445] The
reinforcing materials can be formed from materials selected from
the group consisting of polymeric inorganic materials, nonpolymeric inorganic
materials, polymeric organic materials, nonpolymeric organic materials,
composites
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CA 02647153 2012-12-19
thereof and mixtures thereof that are chemically different from the
polyurethane or
poly(ureaurethane). As used herein, "chemically different" from the
polyurethane or
poly(ureaurethane) means that the reinforcing material has at least one
different atom
or has a different arrangement of atoms compared to the polyurethane or
poly(u reaurethane).
[00446] As used herein, the term "polymeric inorganic material" means a
polymeric material having a backbone repeat unit based on an element or
elements
other than carbon. See James Mark et al., Inorganic Polymers, Prentice Hall
Polymer
Science and Engineering Series, (1992) at page 5. Moreover, as used herein,
the
term "polymeric organic materials" means synthetic polymeric materials,
semisynthetic
polymeric materials and natural polymeric materials, all of which have a
backbone
repeat unit based on carbon.
[00447] An "organic material," as used herein, means carbon-containing
compounds wherein the carbon is typically bonded to itself and to hydrogen,
and often
to other elements as well, and excludes binary compounds such as the carbon
oxides,
the carbides, carbon disulfide, etc.; such ternary compounds as the metallic
cyanides,
metallic carbonyls, phosgene, carbonyl sulfide, etc.; and carbon-containing
ionic
compounds such as metallic carbonates, for example calcium carbonate and
sodium
carbonate. See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th
Ed.
1993) at pages 761-762, and M. Silberberg, Chemistry The Molecular Nature of
Matter
and Change (1996) at page 586.
[00448] As used herein, the term "inorganic material" means any material
that is
not an organic material.
[00449] As used herein, the term "composite material" means a combination
of
two or more differing materials. For example a composite particle can be
formed from
a primary material that is coated, clad or encapsulated with one or more
secondary
materials to form a composite particle that has a softer surface. In some non-
limiting
embodiments, particles formed from composite materials can be formed from a
primary material that is coated, clad or encapsulated with a different form of
the
primary material. For more information on particles useful in the present
invention, see
G. Wypych, Handbook of Fillers, 2nd Ed. (1999) at pages 15-202.
[00450] The reinforcing materials suitable for use in the compositions of
the
invention can comprise inorganic elements or compounds known in the art.
Suitable
nonpolymeric, inorganic reinforcing materials can be formed from ceramic
materials,
metallic materials, and mixtures of any of the foregoing. Nonpolymeric,
inorganic
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CA 02647153 2012-12-19
materials useful in forming the reinforcing materials of the present invention
comprise
inorganic materials selected from the group consisting of graphite, metals,
oxides,
carbides, nitrides, borides, sulfides, silicates, carbonates, sulfates, and
hydroxides.
Suitable ceramic materials comprise metal oxides, metal nitrides, metal
carbides,
metal sulfides, metal silicates, metal borides, metal carbonates, and mixtures
of any of
the foregoing. Non-limiting
examples of suitable metals include molybdenum,
platinum, palladium, nickel, aluminum, copper, gold, iron, silver, alloys, and
mixtures of
any of the foregoing. Non-limiting examples of metal nitrides are, for
example, boron
nitride; non-limiting examples of metal oxides are, for example, zinc oxide;
non-limiting
examples of suitable metal sulfides are, for example, molybdenum disulfide,
tantalum
disulfide, tungsten disulfide, and zinc sulfide; non-limiting examples of
metal silicates
are, for example aluminum silicates and magnesium silicates such as
vermiculite. In
some non-limiting embodiments, the reinforcing material is essentially free of
(less
than 5 weight percent or less than 1 weight percent) or free of fillers such
as sodium
carbonate, calcium carbonate, silicates, alginates, carbon black, and metal
oxides
such as titanium dioxide, silica, and zinc oxide.
[00451] In some non-
limiting embodiments, the reinforcing materials can
comprise a core of essentially a single inorganic oxide such as silica in
colloidal,
fumed, or amorphous form, alumina or colloidal alumina, titanium dioxide,
cesium
oxide, yttrium oxide, colloidal yttria, zirconia, e.g., colloidal or amorphous
zirconia, and
mixtures of any of the foregoing; or an inorganic oxide of one type upon which
is
deposited an organic oxide of another type. In some non-limiting embodiments,
the
reinforcing materials should not seriously interfere with the optical
properties of the
cured composition. As used herein, "transparent" means that the cured coating
has a
BYK Haze index of less than 50 as measured using a BYK/Haze Gloss instrument.
[00452] The
composition can comprise precursors suitable for forming silica
particles in situ by a sol-gel process. The composition according to the
present
invention can comprise alkoxy silanes which can be hydrolyzed to form silica
particles
in situ. For example tetraethylortho silicate can be hydrolyzed with an acid
such as
hydrochloric acid and condensed to form silica particles. Other useful
particles include
surface-modified silicas such as are described in U.S. Pat. No. 5,853,809 at
column 6,
line 51 to column 8, line 43.
[00453] SoIs, such as
an organosols, of reinforcement particles can be used in
the present invention. These sols can be of a wide variety of small-particle,
colloidal
silicas having an average particle size in ranges such as are described below.
The
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CA 02647153 2012-12-19
colloidal silicas can be surface modified during or after the particles are
initially formed.
These surface modified silicas may contain on their surface chemically bonded
carbon-containing moieties, as well as such groups as anhydrous Si02 groups
and
SiOH groups, various ionic groups physically associated or chemically bonded
within
the surface of the silica, adsorbed organic groups, or combinations of any of
the
foregoing, depending on the characteristics of the particular silica desired.
Such
surface modified silicas are described in detail in U.S. Pat. No. 4,680,204.
Such small
particle colloidal silicas are readily available, are essentially colorless
and have
refractive indices which permit their inclusion in compositions that, without
additional
pigments or components known in the art to color and/or decrease the
transparency of
such compositions, result in colorless, transparent compositions or coatings.
[00454] Other suitable non-limiting examples of reinforcing materials
include
colloidal silicas, such as those commercially available from Nissan Chemical
Company
under the trademark ORGANOSILICASOLSTmsuch as ORGANOSILICASOLTM MT-ST,
and from Clariant Corporation as HIGHLINKTM; colloidal aluminas, such as those
commercially available from Nalco Chemical under the trademark NALCO 8676 ;
and
colloidal zirconias, such as those commercially available from Nissan Chemical
Company under the trademark HIT-32M .
[00455] In some non-limiting embodiments of the present invention, the
reinforcing material is a nanostructure. As used herein, the term
"nanostructure" refers
to a three dimensional object wherein the length of the longest dimension
ranges from
1 nm to 1000 nm, for example, from 1 nm to 500 nm, or from 1 nm to 100 nm, or
from
1 to 40 nm.
[00456] Nanostructural reinforcing materials can be incorporated into the
matrix
of a polymer by dispersing pre-made nanostructures, such as for example
nanoclays,
into the polymer solution. Alternatively or additionally, nanostructural
reinforcement
materials can be incorporated into the polymer matrix by forming the
nanostructures in
situ. For example, the nanostructural reinforcement materials can be formed in
situ by
mixing a precursor solution for the polyurethane or poly(ureaurethane) with a
precursor
for the nanostructures to form a mixture, forming nanostructures in the matrix
of the
polymer from the precursor of the nanostructures, and forming a polymer from
the
precursor solution of the polymer.
[00457] As used herein, the phrase "precursor solution for the polyurethane
or
poly(ureaurethane)" refers to any material that can be used as a starting
material to
form the polyurethane or poly(ureaurethane), as discussed above. For example,
if the
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CA 02647153 2012-12-19
desired end product is an aliphatic polyurethane, suitable precursors for the
polymer
include, but are not limited to, 1,4-butanediol, trimethylolpropane, and bis(4-
isocyanatocyclohexyl) methane and thiodiethanol.
[00458] As used
herein, the phrase "precursor for the nanostructures" refers to
any material that can be used as a starting material to form the
nanostructures.
[00459] In some non-
limiting embodiments of the invention, a solvent such as
water, ethanol, iso-propanol, butanol, etc. is added to the mixture.
[00460] The
nanostructures are formed while the viscosity of the polymer is low
so that the nanostructures can incorporate themselves into the matrix of the
polymer.
The formation of the nanostructures can be initiated using various techniques.
In a
non-limiting embodiment of the invention, the nanostructures are formed by
adjusting
the pH of the mixture. An acid or base, such as ammonia, can be used to adjust
the
pH of the solution. Depending on the exact precursor solution of the polymer
and the
exact precursor for the nanostructures, there is an optimum pH range in which
the
nanostructures will form. One of ordinary skill in the art would know what the
optimum
pH range is based on both precursors.
[00461] In another non-
limiting embodiment, the mixture can be heated to
initiate the formation of the nanoparticles. The mixture can be heated to any
temperature provided the mixture is not heated to a temperature above that at
which
the precursor solution would break down. For example, a precursor solution
comprising polyurethane or poly(ureaurethane) cannot be heated above 200 C
because that is the temperature at which polyurethane or poly(ureaurethane)
begins to
decompose. Similarly to the pH range, the optimum temperature range at which
the
particles will form depends on the exact precursor solution of the
polyurethane or
poly(ureaurethane) and the exact precursor for the nanostructures. One of
ordinary
skill in the art would know what the optimum temperature range is based on
both
precursors. Generally, the higher the temperature to which the mixture is
heated
and/or the longer the mixture is heated, the larger the size of the
nanostructures that
will be formed.
[00462] In yet another
non-limiting embodiment of the invention, forming the
nanostructures is accomplished by heating the mixture after the pH of the
mixture is
adjusted. In a further
non-limiting embodiment of the invention, forming the
nanostructures is accomplished by heating the mixture and then adjusting the
pH of
the mixture.
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CA 02647153 2012-12-19
[00463] In various other non-limiting embodiments of the invention, the
nanostructures can be formed by using one or more of the following: increasing
the
pressure on the mixture; by changing the concentration of the precursor
solution for
the polyurethane or poly(ureaurethane); by using an initiator for
nanostructure
formation; and by seeding (adding no greater than 5% of the desired
nanostructure
material based on the projected weight of the formed nanostructures as is well
known
in the art).
[00464] The formed nanostructures are charged species. If the pH of the
solution was adjusted to cause the formation of the nanostructures, the charge
is a
result of the pH adjustment. If no pH adjustment was performed during the
nanostructure formation step, a polymeric stabilizer such as, but not limited
to, sodium
polymethacrylate in water and ammonium polymethacrylate in water, which are
both
commercially available as Darvane 7 and as Darvan C, respectively, from R.T.
Vanderbilt Company, Inc. in Norwalk, CT can be added to the solution to create
the
charge.
[00465] The third step involves forming the polyurethane or
poly(ureaurethane)
from a mixture including the precursor solution of the polyurethane or
poly(ureaurethane). The formation of the polyurethane or poly(ureaurethane)
can be
initiated using various techniques (as discussed in detail above) based on the
precursor solution of the polyurethane or poly(ureaurethane) and the precursor
for the
nanostructures.
[00466] In another embodiment of the present invention, the second and
third
steps described above are switched.
[00467] The method of making polymers having nanostructures incorporated
into the matrix of the polymer according to the present invention is referred
to as an
"in-situ" process. This means the nanostructures are formed during the same
process
that produces the polymer as opposed to pre-formed nanostructures being
dispersed
into a polymer solution.
[00468] During some methods of the present invention, ions (cations and/or
anions) can form in the mixture. The formed ions and other process variables,
such as
the pressure of the system in which the mixture is held, can affect the final
polymer.
For example, the amount of nanostructure formation and the morphology of the
nanostructures will vary depending on the types and amount of ions present in
the
solution.
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CA 02647153 2012-12-19
[00469] In the polymer matrix, the nanostructures typically continually
approach
one another and collide because they possess kinetic energy. Under normal
circumstances, some of the nanostructures would become bound together and
agglomerate due to various forces such as Van der Waals forces. As discussed
above, agglomeration is not desirable because the nanostructures can
effectively
become regular sized particles and the desired effect of incorporating the
nanostructures is reduced.
[00470] However, the methods described above can produce polymers having
nanostructures in the matrix of the polymer that do not agglomerate to the
extent that
the performance of the polymer is compromised, for example to improve the
thermal
stability of polymer and/or to decrease the chemical activity of polymer. The
nanostructures do not agglomerate because they are stabilized. The
stabilization can
occur via electrostatic stabilization and/or steric stabilization.
[00471] Because the nanostructures in the polymer matrix are similarly
charged
species, they repel each other. This prevents the nanostructures from coming
so
close together that they agglomerate. This phenomenon is referred to as
electrostatic
stabilization.
[00472] Because the nanostructures are surrounded by polymer precursor
solution when they are formed, the nanostructures lose a degree of freedom
which
they would otherwise possess as the nanostructures approach each other. This
loss
of freedom is expressed, in thermodynamic terms, as a reduction in entropy,
which
provides the necessary barrier to hinder agglomeration. This phenomenon is
referred
to as steric stabilization. The same principle applies when the method
involves
forming the polymer before forming the nanostructures.
[00473] The concentration of the nanostructures in the polymer matrix can
range from 0.1% to 90%, for example from 3% to 85% or from 15% to 80% based on
total volume. The nanostructures in the polymer matrix can have the following
shapes:
spherical, polyhedral-like cubic, triangular, pentagonal, diamond shaped,
needle
shaped, rod shaped, disc shaped etc. The nanostructures in the polymer matrix
can
have an aspect ratio 01 1:1 to 1:1,000, for example 1:1 to 1:100.
[00474] Non-limiting examples of suitable nanostructure materials include
titania, alumina, indium tin oxide (ITO), antimony tin oxide (ATO), monobutyl
tin tri-
chloride, indium acetate, and antimony tri-chloride nanostructures
incorporated into the
polymer matrix is formed. Suitable precursors for titania nanostructures
include, but
are not limited to, titanium iso-propoxide, titanium (I\/) chloride and
potassium titanyl
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CA 02647153 2012-12-19
oxalate. Suitable precursors for alumina nanostructures include, but are not
limited to,
aluminum iso-propoxide, aluminum tri-tert-butoxide, aluminum tri-sec-butoxide,
aluminum triethoxide, and aluminum pentanedionate. Suitable precursors for
zirconia
nanostructures include, but are not limited to, zirconium iso-propoxide,
zirconium tert-
butoxide, zirconium butoxide, zirconium ethoxide, zirconium 2,4-
pentanedionate, and
zirconium trifluoropentane-dionate.
[00475] In the first step, a precursor solution for polyurethane or
poly(ureaurethane) is mixed with a precursor for the nanostructures.
[00476] In the second step, nanostructures are formed from the precursor of
the
nanostructures in the polymer matrix. The nanostructure formation can be
caused by
adjusting the pH of the mixture followed by heating. The pH can be adjusted by
introducing an agent, such as ammonia, into the mixture. For ITO
nanostructures in a
urethane or ureaurethane aqueous solution, the nanostructures begin to form at
a pH
> 8. After the pH is adjusted, the mixture is heated to a temperature of up to
100 C.
Heating the solution to a temperature greater than 100 C may cause the polymer
matrix to decompose. As discussed above, heating the mixture for a longer time
period can increase the size of the nanostructures.
[00477] In the third step, the precursor solution for the polymer is
converted to
the polymer, as discussed above for forming the polyurethane and
poly(ureaurethane).
[00478] In a non-limiting embodiment of the invention, the final reinforced
polymer is used as an interlayer in a laminated glass transparency for
automotive and
architectural applications. As is well known in the art, a laminated glass
transparency
can be manufactured by interposing an interlayer between at least two
transparent
glass sheets.
[00479] In this particular embodiment of the invention, a laminated glass
transparency for an automotive and architectural applications embodiment, it
is
important that the nanostructures do not agglomerate. If the nanostructures
were to
agglomerate and effectively achieve a diameter of greater than 200 nm, the
nanostructures would scatter visible light rays to such an extent that
transmittance
through the interlayer would be insufficient for the application. A polymer
with
nanostructures having an acceptable size for the application, can be
determined using
a "haze value". The haze value is associated with the degree to which
transparency is
prevented. The larger the nanostructures present in the polymer matrix, the
higher the
haze value. According to the present invention, laminated glass for automotive
and
architectural applications has a haze value of less than or equal to about 1%,
for
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CA 02647153 2012-12-19
example, less than or equal to about 0.3%, or less than or equal to about
0.2%, as
measured using a Hazeguard System from BYK-Gardner in Columbia, MD.
[00480] In the embodiment where a polyurethane or poly(ureaurethane) is
being formed having titania nanostructures incorporated into the polymer
matrix, the
first step can comprise mixing titanium iso-propoxide with a 1-10 wt% H202
solution
and suitable polyurethane or poly(ureaurethane) precursors as discussed above.
The
H202 acts as an initiator for titania nanostructures; particularly, titania
nanostructures
in the anatase form. Optionally, polymers such as polyoxyethylene (20)
sorbitan
monooleate commercially available as Tweene 80 from ICI Ltd. (Bridgewater, NJ)
can
be added to the solution to help stabilize the titania nanostructures.
[00481] In the second step, the titania nanostructures are formed from the
precursor by heating the mixture to a temperature of up to 100 C.
[00482] In the third step, the precursor solution for the polymer is
converted into
polyurethane or poly(ureaurethane) as discussed in detail above.
[00483] In a non-limiting embodiment of the invention, polyurethane or
poly(ureaurethane) having titania, alumina, or zirconia nanostructures
incorporated
into the matrix of the polymer can be used as an optical lens. A polymer with
nanostructures having an acceptable size for optical lens applications can be
determined using a "haze value". According to the present invention, an
optical lens
has a haze value of less than or equal to 0.5%, for example less than or equal
to 0.2%,
as measured using a Hazeguard System from BYK Gardner.
[00484] In a non-limiting embodiment of the invention, a polyurethane
having
ITO or ATO nanostructures incorporated into the polymer matrix is formed. Such
a
polymer can be formed in the following manner. In the first step, a precursor
solution
for the trimethylol propane, methylene bis(4-cyclohexylisocyanate) and
thiodiethanol is
mixed with a precursor for ITO or ATO nanostructures.
[00485] A suitable precursor solution for the polyurethane is trimethylol
propane,
methylene bis(4-cyclohexylisocyanate), thiodiethanol includes, but is not
limited to,
1, 4-butanediol. Suitable precursors for ITO nanostructures include monobutyl
tin tri-
chloride and indium acetate. A suitable precursor for ATO nanostructures is
antimony
tri-chloride.
[00486] In the second step, ITO or ATO nanostructures are formed from the
precursor. The nanostructure formation can be caused by adjusting the pH of
the
solution by introducing an agent, such as ammonia, into the mixture followed
by
heating the mixture. For ITO nanostructures, the ITO nanostructures start to
form at
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CA 02647153 2012-12-19
pH > 8. After the pH is adjusted, the mixture is heated to a temperature of up
to
100 C. As discussed above, heating the mixture for a longer time period can
increase
the size of the nanostructures.
[00487] In the third step, the 1,4-butanediol is mixed into trimethylol
propane,
methylene bis(4-cyclohexylisocyanate), thiodiethanol as is well known in the
art. For
example, 1,4 butanediol, thiodiethanol, trimethylol propane (TMP), and
DESMODUR
W can all be mixed into a vessel and heated to 180 F. The mixture is mixed
under
vacuum for approximately 15 minutes, and then a tin catalyst, such as
dibutyltindilaurate or bismuth carboxylate, is added to the mixture in a 25
ppm
concentration. The mixture is then cast into a glass mold and cured for at
least 20
hours at 250 F (121 C) to form the polyurethane.
[00488] In a non-limiting embodiment, trimethylol propane, methylene bis(4-
cyclohexylisocyanate), thiodiethanol having ITO or ATO nanostructures
incorporated
into the polymer matrix is used to form an anti-static coating for aircraft
windows. The
polymer with the nanostructures has an elastic modulus that is greater than
that of the
standard trimethylol propane, methylene bis(4-cyclohexylisocyanate)
thiodiethanol
without ITO/ATO nanoparticles.
[00489] In other non-limiting embodiments, the reinforcement material is a
nanostructural reinforcement material formed in situ by swelling the
polyurethane in a
solvent comprising a precursor for the nanostructures, and forming
nanostructures in
the matrix of the polyurethane from the precursor of the nanostructures. Non-
limiting
examples of suitable solvents for mild swelling of the polymer include
methanol,
propylene glycol methyl ether such as DOWANOLTM PM (commercially available
from
Dow Chemical Co. of Midland, Michigan), diacetone alcohol, 2-propanol, 1-
propanol
and acetylpropanol.
[00490] A polymer with nanostructures having an acceptable size for the
aircraft
window application can be determined using a "haze value". According to the
present
invention, a laminated aircraft window has a haze value of less than or equal
to about
1%, for example less than or equal to about 0.5%, as measured using a
Hazeguard
System from BYK Gardner.
[00491] In some non-limiting embodiments of the present invention, the
reinforcing materials have a hardness value greater than the hardness value of
materials that can abrade a polymeric coating or a polymeric substrate.
Examples of
materials that can abrade the polymeric coating or polymeric substrate
include, but are
not limited to, dirt, sand, rocks, glass, carwash brushes, and the like. The
hardness
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CA 02647153 2012-12-19
values of the particles and the materials that can abrade the polymeric
coating or
polymeric substrate can be determined by any conventional hardness measurement
method, such as Vickers or Brinell hardness, or can be determined according to
the
original Mohs' hardness scale which indicates the relative scratch resistance
of the
surface of a material on a scale of one to ten. The Mohs' hardness values of
several
nonlimiting examples of particles formed from inorganic materials suitable for
use in
the present invention are given in Table 1 below.
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TABLE A
Particle material Mohs' hardness (original scale)
Boron nitride 2'
Graphite 0.5-12
Molybdenum disulfide 13
Talc 1-1.54
Mica 2.8-3.25
Kaolinite 2.0-2.56
Gypsum 1.6-27
Calcite (calcium carbonate) 35
Calcium fluoride 49
Zinc oxide 4.510
Aluminum 2.511
Copper 2.5_312
Iron 4-513
Gold 2.5-314
Nickel 515
Palladium 4.816
Platinum 4.317
Silver 2.5-418
Zinc sulfide 3.549
1 K. Ludema, Friction, Wear, Lubrication, (1996) at page 27.
2R. Weast (Ed.), Handbook of Chemistry and Physics, CRC Press (1975) at page F-
22.
3 R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at
page
793,.
4 Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 1113.
Hawley's Condensed Chemical Dictionary, (12th Ed. 1993) at page 784.
6 Handbook of Chemistry and Physics at page F-22.
7 Handbook of Chemistry and Physics at page F-22.
8 Friction, Wear, Lubrication at page 27.
9 Friction, Wear, Lubrication at page 27.
19 Friction, Wear, Lubrication at page 27.
11 Friction, Wear, Lubrication at page 27.
12 Handbook of Chemistry and Physics at page F-22.
13 Handbook of Chemistry and Physics at page F-22.
14 Handbook of Chemistry and Physics at page F-22.
Handbook of Chemistry and Physics at page F-22.
16 Handbook of Chemistry and Physics at page F-22.
17 Handbook of Chemistry and Physics at page F-22.
18 Handbook of Chemistry and Physics at page F-22.
19 R. Weast (Ed.), Handbook of Chemistry Physics, CRC Press (71st Ed.
1990) at
page 4-158
[00492] In some non-limiting embodiments, the reinforcing material can be
formed from a primary material that is coated, clad or encapsulated with one
or more
secondary materials to form a composite material that has a harder surface. In
other
non-limiting embodiments, reinforcement particles can be formed from a primary
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CA 02647153 2012-12-19
material that is coated, clad or encapsulated with a differing form of the
primary
material to form a composite material that has a harder surface.
[00493] In some non-limiting examples, inorganic particles formed from an
inorganic material such as silicon carbide or aluminum nitride can be provided
with a
silica, carbonate or nanoclay coating to form a useful composite particle. In
other
nonlimiting examples, a silane coupling agent with alkyl side chains can
interact with
the surface of an inorganic particle formed from an inorganic oxide to provide
a useful
composite particle having a "softer" surface. Other examples include cladding,
encapsulating or coating particles formed from nonpolymeric or polymeric
materials
with differing nonpolymeric or polymeric materials. One non-limiting example
of such
composite particles is DUALITETm, which is a synthetic polymeric particle
coated with
calcium carbonate that is commercially available from Pierce and Stevens
Corporation
of Buffalo, N.Y.
[00494] In some non-limiting embodiments, the particles are formed from
solid
lubricant materials. As used herein, the term "solid lubricant" means any
solid used
between two surfaces to provide protection from damage during relative
movement
and/or to reduce friction and wear. In some non-limiting embodiments, the
solid
lubricants are inorganic solid lubricants. As used herein, "inorganic solid
lubricant"
means that the solid lubricants have a characteristic crystalline habit which
causes
them to shear into thin, flat plates which readily slide over one another and
thus
produce an antifriction lubricating effect. See R. Lewis, Sr., Hawley's
Condensed
Chemical Dictionary, (12th Ed. 1993) at page 712. Friction is the resistance
to sliding
one solid over another. F. Clauss, Solid Lubricants and Self-Lubricating
Solids (1972)
at page 1.
[00495] In some non-limiting embodiments, the particles have a lamellar
structure. Particles having a lamellar structure are composed of sheets or
plates of
atoms in hexagonal array, with strong bonding within the sheet and weak van
der
Waals bonding between sheets, providing low shear strength between sheets. A
non-
limiting example of a lamellar structure is a hexagonal crystal structure.
Inorganic solid
particles having a lamellar fullerene (i.e., buckyball) structure can also be
useful in the
present invention.
[00496] Non-limiting examples of suitable materials having a lamellar
structure
that are useful in forming the particles of the present invention include
boron nitride,
graphite, metal dichalcogenides, mica, talc, gypsum, kaolinite, calcite,
cadmium iodide,
silver sulfide, and mixtures of any of the foregoing. Suitable metal
dichalcogenides
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CA 02647153 2012-12-19
include molybdenum disulfide, molybdenum diselenide, tantalum disulfide,
tantalum
diselenide, tungsten disulfide, tungsten diselenide, and mixtures of any of
the
foregoing.
[00497] In some non-
limiting embodiments, the reinforcing material can be glass
fiber strands. The glass fiber strands are formed from glass filaments, a
class of
filaments generally accepted to be based upon oxide compositions such as
silicates
selectively modified with other oxide and non-oxide compositions. Useful glass
filaments can be formed from any type of fiberizable glass composition known
to those
skilled in the art, and include those prepared from fiberizable glass
compositions such
as "E-glass", "A-glass", "C-glass", "D-glass", "R-glass", "S-glass", and E-
glass
derivatives that are fluorine-free and/or boron-free. As used herein, the term
"fiberizable" means a material capable of being formed into a generally
continuous
filament, fiber, strand or yarn. As used herein, "E-glass derivatives" means
glass
compositions that include minor amounts of fluorine and/or boron or can be
fluorine-
free and/or boron-free. Furthermore, as used herein, "minor amounts of
fluorine"
means less than 0.5 weight percent fluorine, or less than 0.1 weight percent
fluorine,
and "minor amounts of boron" means less than 5 weight percent boron, or less
than 2
weight percent boron. Basalt and mineral wool are examples of other
fiberizable glass
materials useful in the present invention. Non-limiting examples of suitable
non-glass
fiberizable inorganic materials include ceramic materials such as silicon
carbide,
carbon, quartz, graphite, mullite, aluminum oxide and piezoelectric ceramic
materials.
In some non-limiting embodiments, the glass filaments are formed from E-glass.
Such
compositions and methods of making glass filaments therefrom are well known to
those skilled in the art, such glass compositions and fiberization methods are
disclosed
in K. Loewenstein, The Manufacturinq Technoloqy of Continuous Glass Fibres,
(3d Ed.
1993) at pages 30-44, 47-60, 115-122 and 126-135.
[00498] The glass
fibers can have a nominal filament diameter ranging from
about 5.0 to about 30.0 micrometers (corresponding to a filament designation
of D
through Y). Typically, the glass fiber strands have a strand coating
composition which
is compatible with the composition applied to at least a portion of surfaces
of the glass
fiber strands, such as an essentially dried residue. The glass
fiber strand
reinforcements can be used in chopped form, generally continuous strands,
mats, etc.
[00499] The particles
also can be hollow particles formed from materials
selected from polymeric and nonpolymeric inorganic materials, polymeric and
nonpolymeric organic materials, composite materials, and mixtures of any of
the
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CA 02647153 2012-12-19
foregoing. Non-limiting examples of suitable materials from which the hollow
particles
can be formed are described above. In some embodiments, the hollow particles
are
hollow glass spheres.
[00500] In some non-limiting embodiments, the reinforcing materials can be
formed from nonpolymeric, organic materials. Nonlimiting examples of
nonpolymeric,
organic materials useful in the present invention include, but are not limited
to,
stearates (such as zinc stearate and aluminum stearate), diamond, carbon
black, and
stearamide.
1005011 In some non-limiting embodiments, the particles can be formed from
inorganic polymeric materials. Nonlimiting examples of useful inorganic
polymeric
materials include polyphosphazenes, polysilanes, polysiloxane, polygeremanes,
polymeric sulfur, polymeric selenium, silicones, and mixtures of any of the
foregoing.
A non-limiting example of a particle formed from an inorganic polymeric
material
suitable for use in the present invention is TOSPEARLTm 1, which is a particle
formed
from cross-linked siloxanes and is commercially available from Toshiba
Silicones
Company, Ltd. of Japan.
[00502] The particles can be formed from synthetic, organic polymeric
materials
that are chemically different from the polyurethane or poly(ureaurethane).
Nonlimiting
examples of suitable organic polymeric materials include, but are not limited
to,
thermoset materials and thermoplastic materials. Nonlimiting examples of
suitable
thermoplastic materials include thermoplastic polyesters such as polyethylene
terephthalate, polybutylene terephthalate, and polyethylene naphthalate,
polycarbonates, polyolefins such as polyethylene, polypropylene, and
polyisobutene,
acrylic polymers such as copolymers of styrene and an acrylic acid monomer,
and
polymers containing methacrylate, polyamides, thermoplastic polyurethanes,
vinyl
polymers, and mixtures of any of the foregoing.
[00503] In some non-limiting embodiments, the polymeric organic material is
a
(meth)acrylic polymer or copolymer comprising at least one functional group
selected
from the group consisting of silane groups, carboxyl groups, hydroxyl groups
and
amide groups. In some non-limiting embodiments, these meth)acrylic polymer or
copolymers can be present as nanofibers having a diameter up to about 5000 nm,
such as about 5 to about 5000 nm, or less than the wavelength of visible
light, for
See R. J. Perry "Applications for Cross-Linked Siloxane Particles" Chemtech.
February 1999
at pp. 39-44.
¨ 117 ¨
CA 02647153 2012-12-19
example 700 nanometers or less, such as about 50 to about 700 nanometers.. The
fibers may have a ribbon shape and in this case diameter is intended to mean
the
largest dimension of the fiber. Typically the width of the ribbon shaped
fibers can be
up to about 5000 nanometers, such as about 500 to about 5000 nm and the
thickness
up to about 200 nm, such as about 5 to about 200 nm. The fibers can be
prepared by
electrospinning a ceramic melt, a polymer melt or a polymer solution.
[00504] Suitable (meth)acrylic polymers can be made by addition
polymerization
of unsaturated polymerizable materials that contain silane groups, carboxyl
groups,
hydroxyl groups and amine or amide groups. Non-limiting examples of useful
silane
groups include groups that have the structure Si-X (wherein n is an integer
having a
value ranging from 1 to 3 and X is selected from chlorine, alkoxy esters,
and/or acyloxy
esters). Such groups hydrolyze in the presence of water including moisture in
the air
to form silanol groups that condense to form ¨Si-O-Si- groups. The
(meth)acrylic
polymer can contain hydroxyl functionality, for example by using a hydroxyl
functional
ethylenically unsaturated polymerizable monomer such as hydroxyalkyl esters of
(meth)acrylic acids having from 2 to 4 carbon atoms in the hydroxyalkyl group.
The
(meth)acrylic polymer optionally contains nitrogen functionality introduced
from
nitrogen-containing ethylenically unsaturated monomers, such as amines,
amides,
ureas, imidazoles and pyrrolidones. Further discussion of such (meth)acrylic
polymers
and fiberizing methods are disclosed in U.S. Patent No. 7,632,563 entitled
"Transparent Composite Articles" and U.S. Patent No. 7,589,141 entitled
"Organic-
Inorganic Polymer Composites and Their Preparation by Liquid Infusion", each
filed
concurrently herewith.
[00505] Non-limiting examples of suitable fiberizable organic materials
include
cotton, cellulose, natural rubber, flax, ramie, hemp, sisal and wool. Non-
limiting
examples of suitable fiberizable organic polymeric materials include those
formed from
polyamides (such as nylon and aramids)(such as KEVLARTM aramid fibers),
thermoplastic polyesters (such as polyethylene terephthalate and polybutylene
terephthalate), acrylics (such as polyacrylonitriles), polyolefins,
polyurethanes and
vinyl polymers (such as polyvinyl alcohol). Non-glass fiberizable materials
useful in
the present invention and methods for preparing and processing such fibers are
discussed at length in the Encyclopedia of Polymer Science and Technology,
Vol. 6
(1967) at pages 505-712.
[00506] It is understood that blends or copolymers of any of the above
materials
and combinations of fibers formed from any of the above materials can be used
in the
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CA 02647153 2012-12-19
present invention, if desired. Moreover, the term strand can encompass at
least two
different fibers made from differing fiberizable materials. As used herein,
the term
"fiberizable" means a material capable of being formed into a generally
continuous
filament, fiber, strand or yarn.
[00507] Suitable thermoplastic fibers can be formed by a variety of polymer
extrusion and fiber formation methods, such as for example drawing, melt
spinning,
dry spinning, wet spinning and gap spinning. Such methods are well known to
those
skilled in the art and further discussion thereof is not believed to be
necessary in view
of the present disclosure. If additional information is needed, such methods
are
disclosed in Encyclopedia of Polymer Science and Technology, Vol. 6 at 507-
508.
[00508] Non-limiting examples of useful polyamide fibers include nylon
fibers
such as nylon 6 (a polymer of caprolactam), nylon 6,6 (a condensation product
of
adipic acid and hexamethylenediamine), nylon 12 (which can be made from
butadiene)
and nylon 10, polyhexamethylene adipamide, polyamide-imides and aramids such
as
KEVLARTM, which is commercially available from E. I. duPont de Nemours, Inc.
of
Wilmington, Del.
[00509] Non-limiting examples of useful thermoplastic polyester fibers
include
those composed of polyethylene terephthalate and polybutylene terephthalate.
[00510] Non-limiting examples of useful fibers formed from acrylic polymers
include polyacrylonitriles having at least about 35% by weight acrylonitrile
units, or at
least about 85% by weight, which can be copolymerized with other vinyl
monomers
such as vinyl acetate, vinyl chloride, styrene, vinylpyridine, acrylic esters
or
acrylamide. See Encyclopedia of Polymer Science and Technology, Vol. 6 at 559-
561.
[00511] Non-limiting examples of useful polyolefin fibers are generally
composed of at least 85% by weight of ethylene, propylene, or other
olefins. See Encyclopedia of Polymer Science and Technology, Vol. 6 at 561-
564.
[00512] Non-limiting examples of useful fibers formed from vinyl polymers
can
be formed from polyvinyl chloride, polyvinylidene chloride,
polytetrafluoroethylene, and
polyvinyl alcohol.
[00513] Further non-limiting examples of thermoplastic fiberizable
materials
believed to be useful in the present invention include fiberizable polyimides,
polyether
sulfones, polyphenyl sulfones, polyetherketones, polyphenylene oxides,
polyphenylene
sulfides and polyacetals.
[00514] It is understood that blends or copolymers of any of the above
materials
and combinations of fibers formed from any of the above materials can be used
in the
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CA 02647153 2012-12-19
present invention, if desired. Also, the thermoplastic fibers can have an
antistatic
agent coated thereon.
[00515] Suitable reinforcing materials can include mats or fabrics
comprised of
any of the fibers discussed above. An increasingly popular process for forming
composites is by compression molding or stamping a moldable sheet of a
thermoplastic resin reinforced with fibers such as a glass fiber mat, often
referred to as
glass mat thermoplastics or "GMT". These composite sheets can be used to form
articles such as automobile components and housings for computers. An example
of
a commercially successful GMT sheet is the AZDELO moldable composite sheet
which is formed by extruding layers of polypropylene resin sheet with needled
mats of
continuous glass fiber strand. The AZDELS composite sheet is commercially
available
from Azdel, Inc. of Shelby, N.C.
[00516] For reinforcing a resin matrix material, U.S. Pat. Nos. 3,664,909,
3,713,962 and 3,850,723 disclose fibrous mats of unstranded filaments which
can be
layered with reinforcing mats of fiber strands.
[00517] U.S. Pat. No. 4,847,140 discloses an insulation medium formed by
needling a loose layer of inorganic fibers, such as glass, bonded together by
a carrier
web which is a blend of inorganic and organic fibers, with the carrier web
comprising
up to about 10% by weight organic fibers.
[00518] U.S. Pat. Nos. 4,948,661, 5,011,737, 5,071,608 and 5,098,624
disclose
fiber reinforced thermoplastic molded products produced by intimately blending
reinforcing glass fibers and thermoplastic fibers into a web and heating the
web to the
melting point of the thermoplastic fibers while applying pressure to the web
to press
the web into a consolidated structure.
[00519] A non-limiting example of a useful polypropylene spun-bonded fiber
mat
is commercially available from Fiberweb N.A., Inc. of Simpsonville, S.C.
[00520] Nonlimiting examples of suitable thermoset reinforcement materials
include thermoset polyesters, vinyl esters, epoxy materials, phenolics,
aminoplasts,
thermoset polyurethanes, and mixtures of any of the foregoing. A specific,
nonlimiting
example of a synthetic polymeric particle formed from an epoxy material is an
epoxy
microgel particle.
[00521] The concentration of reinforcement particles present in the cured
article
or coating can be determined, if desired, by a variety of analysis techniques
well
known in the art, such as Transmission Electron Microscopy ("TEM"), Surface
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CA 02647153 2012-12-19
Scanning Electron Microscopy ("X-SEM"), Atomic Force Microscopy ("AFM"), and X-
ray Photoelectron Spectroscopy.
[00522] In some non-limiting embodiments, the present invention is directed
to
cured compositions as previously described wherein the reinforcement particles
have
an average particle size of less than about 100 microns prior to incorporation
into the
composition, or less than about 50 microns prior to incorporation into the
composition.
In other non-limiting embodiments, the present invention is directed to cured
compositions as previously described wherein the reinforcement particles have
an
average particle size ranging from about 1 to less than about 1000 nanometers
prior to
incorporation into the composition, or about 1 to about 100 nanometers prior
to
incorporation into the composition.
[00523] In other non-limiting embodiments, the present invention is
directed to
cured compositions as previously described wherein the particles have an
average
particle size ranging from about 5 to about 50 nanometers prior to
incorporation into
the composition, or about 5 to about 25 nanometers prior to incorporation into
the
composition.
[00524] In an embodiment where the average particle size of the particles
is at
least about one micron, the average particle size can be measured according to
known
laser scattering techniques. For example the average particle size of such
particles is
measured using a Horiba Model LA 900 laser diffraction particle size
instrument, which
uses a helium-neon laser with a wave length of 633 nm to measure the size of
the
particles and assumes the particle has a spherical shape, i.e., the "particle
size" refers
to the smallest sphere that will completely enclose the particle.
[00525] In an embodiment of the present invention wherein the size of the
particles is less than or equal to one micron, the average particle size can
be
determined by visually examining an electron micrograph of a transmission
electron
microscopy ("TEM") image, measuring the diameter of the particles in the
image, and
calculating the average particle size based on the magnification of the TEM
image.
One of ordinary skill in the art will understand how to prepare such a TEM
image, and
a description of one such method is disclosed in the examples set forth below.
In one
nonlimiting embodiment of the present invention, a TEM image with 105,000X
magnification is produced, and a conversion factor is obtained by dividing the
magnification by 1000. Upon visual inspection, the diameter of the particles
is
measured in millimeters, and the measurement is converted to nanometers using
the
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CA 02647153 2012-12-19
conversion factor. The diameter of the particle refers to the smallest
diameter sphere
that will completely enclose the particle.
[00526] The shape (or morphology) of the reinforcing material can vary
depending upon the specific embodiment of the present invention and its
intended
application. For example generally spherical morphologies (such as solid
beads,
microbeads, or hollow spheres), can be used, as well as particles that are
cubic, platy,
or acicular (elongated or fibrous). Additionally, the particles can have an
internal
structure that is hollow, porous or void free, or a combination of any of the
foregoing,
e.g., a hollow center with porous or solid walls. For more information on
suitable
particle characteristics see H. Katz et al. (Ed.), Handbook of Fillers and
Plastics (1987)
at pages 9-10.
[00527] It will be recognized by one skilled in the art that mixtures of
one or
more particles having different average particle sizes can be incorporated
into the
compositions in accordance with the present invention to impart the desired
properties
and characteristics to the compositions. For example particles of varying
particle sizes
can be used in the compositions according to the present invention.
[00528] In some non-limiting embodiments, the reinforcing material(s) are
present in the composition in an amount ranging from about 0.01 to about 75
weight
percent, or about 25 to about 50 weight percent, based on total weight of the
components which form the composition.
[00529] Reinforcement particles can be present in a dispersion, suspension
or
emulsion in a carrier. Nonlimiting examples of suitable carriers include, but
are not
limited to, water, solvents, surfactants, or a mixture of any of the
foregoing.
Nonlimiting examples of suitable solvents include, but are not limited to,
mineral oil,
alcohols such as methanol or butanol, ketones such as methyl amyl ketone,
aromatic
hydrocarbons such as xylene, glycol ethers such as ethylene glycol monobutyl
ether,
esters, aliphatics, and mixtures of any of the foregoing.
[00530] Dispersion techniques such as grinding, milling, microfluidizing,
ultrasounding, or any other dispersing techniques well known in the art of
coatings or
molded article formulation can be used. Alternatively, the particles can be
dispersed
by any other dispersion techniques known in the art. If desired, the particles
in other
than colloidal form can be post-added to an admixture of other composition
components and dispersed therein using any dispersing techniques known in the
art.
[00531] A further embodiment of the present invention is directed to a
coated
automobile substrate comprising an automobile substrate and a cured
composition
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CA 02647153 2012-12-19
coated over at least a portion of the automobile substrate, wherein the cured
composition is selected from any of the foregoing compositions. In yet another
embodiment, the present invention is directed to a method of making a coated
automobile substrate comprising providing an automobile substrate and applying
over
at least a portion of the automotive substrate a coating composition selected
from any
of the foregoing compositions. Again, the components used to form the cured
compositions in these embodiments can be selected from the components
discussed
above, and additional components also can be selected from those recited
above.
[00532] Suitable flexible elastomeric substrates can include any of the
thermoplastic or thermoset synthetic materials well known in the art.
Nonlimiting
examples of suitable flexible elastomeric substrate materials include
polyethylene,
polypropylene, thermoplastic polyolefin ("TPO"), reaction injected molded
polyurethane
("RIM"), and thermoplastic polyurethane ("TPU").
[00533] Nonlimiting examples of thermoset materials useful as substrates
for
coating with compositions of the present invention include polyesters,
epoxides,
phenolics, polyurethanes such as "RIM" thermoset materials, and mixtures of
any of
the foregoing. Nonlimiting examples of suitable thermoplastic materials
include
thermoplastic polyolefins such as polyethylene, polypropylene, polyamides such
as
nylon, thermoplastic polyurethanes, thermoplastic polyesters, acrylic
polymers, vinyl
polymers, polycarbonates, acrylonitrile-butadiene-styrene ("ABS") copolymers,
ethylene propylene diene terpolymer ("EPDM") rubber, copolymers, and mixtures
of
any of the foregoing.
[00534] Nonlimiting examples of suitable metal substrates useful as
substrates
for coating with compositions of the present invention include ferrous metals
(e.g., iron,
steel, and alloys thereof), nonferrous metals (e.g., aluminum, zinc,
magnesium, and
alloys thereof), and mixtures of any of the foregoing. In the particular use
of
automobile components, the substrate can be formed from cold rolled steel,
electrogalvanized steel such as hot dip electrogalvanized steel,
electrogalvanized iron-
zinc steel, aluminum, and magnesium.
[00535] When the substrates are used as components to fabricate automotive
vehicles (including, but not limited to, automobiles, trucks and tractors)
they can have
any shape, and can be selected from the metallic and flexible substrates
described
above. Typical shapes of automotive body components can include bodies
(frames),
hoods, doors, fenders, mirror housings, bumpers, and trim for automotive
vehicles.
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[00536] In embodiments
of the present invention directed to automotive
applications, the cured compositions can be, for example, the
electrodeposition
coating, the primer coating, the basecoat and/or the topcoat. Suitable
topcoats include
monocoats and basecoat/clearcoat composites. Monocoats are formed from one or
more layers of a colored coating composition.
[00537] In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of Groups A-P can be reinforced with fiberglass to form a
composite article, such as for example a windmill blade, blast-resistant
panels, bullet
resistant panels and radomes.
Group R
[00538] In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of Groups A-Q can be useful as one or more layers in a
multilayer
article. If desired, the multilayered article can be laminated.
[00539] In some non-
limiting embodiments, the polymer is cut while warm,
granulated, extruded and/or milled and calendered to sheets and assembled into
laminates and aged for several days, a week, or longer at ambient temperature
(about
25 C).
[00540] In some non-
limiting embodiments, the present invention provides
articles having multiple layers of polyurethanes and/or poly(ureaurethanes) of
the
present invention. The thickness of each layer and overall thickness of the
article can
vary as desired. Non-limiting examples of suitable thicknesses of the layers
and
articles are discussed below. The layers can be laminated together, if
desired.
[00541] In some non-
limiting embodiments, the present invention provides
multilayered articles or laminates comprising: (a) at least one layer of the
polyurethane(s) or poly(ureaurethane)s of the present invention as discussed
above;
and (b) at least one layer of a substrate selected from the group consisting
of paper,
glass, ceramic, wood, masonry, textile, metal or organic polymeric material
and
combinations thereof. In some non-
limiting embodiments, the layer (a) of
polyurethane(s) or poly(ureaurethane)s of the present invention is chemically
or
physically different from the organic polymeric material of layer (b), i.e.,
it has at least
one different atom, arrangement of atoms or configuration. In other
embodiments, two
or more layers of the same or similar polyurethane(s) or poly(ureaurethane)s
of the
present invention can be used.
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1005421 In some non-
limiting embodiments, the substrate is an optically clear
polymerized organic material prepared from a thermoplastic polycarbonate
resin, such
as the carbonate-linked resin derived from bisphenol A and phosgene, which is
sold
under the trademark LEXAN by GE Plastics of Pittsfield, Massachusetts; a
polyester,
such as the material sold under the trademark MYLARTM by E.I. duPont de
Nemours
Co. of Wilmington, Delaware; a poly(methyl methacrylate), such as the material
sold
under the trademark PLEXIGLASTm by Altuglas International of Philadelphia,
Pennsylvania; polyhexylene-polycarbonate-based polyurethanes; polymerizates of
a
polyol(ally1 carbonate) monomer, especially diethylene glycol bis(ally1
carbonate),
which monomer is sold under the trademark CR39TM by PPG Industries, Inc., and
polymerizates of copolymers of a polyol (allyl carbonate), e.g., diethylene
glycol
bis(ally1 carbonate), with other copolymerizable monomeric materials, such as
copolymers with vinyl acetate, and copolymers with a polyurethane having
terminal
diacrylate functionality, as described in U.S. Pat. Nos. 4,360,653 and
4,994,208; and
copolymers with aliphatic urethanes, the terminal portion of which contain
allyl or
acrylyl functional groups, as described in U.S. Pat. No. 5,200,483; poly(vinyl
acetate),
polyvinylbutyral, polyurethane, polymers of members of the group consisting of
diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and
ethoxylated trimethylol propane triacrylate monomers; cellulose acetate,
cellulose
propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene and
copolymers
of styrene with methyl methacrylate, vinyl acetate and acrylonitrile.
1005431 A non-limiting
example of a suitable polyhexylene-polycarbonate-based
polyurethane can be prepared as follows: a hydroxyl - terminated prepolymer is
made
from 0.2 equivalents of a 1000 molecular weight hexanediol ¨ based carbonate
diol
(PC-1733 commercially available from Stahl), 0.8 equivalents of 1,5
pentanediol, and
1.0 equivalents of trimethylhexanediisocyanate. The components are heated to
180 F
(82 C) and using 100 ppm of dibutyltin dilaurate as a catalyst. The prepolymer
has an
equivalent weight of 218 grams/equivalent. The trimeric
hydroxyl terminated
prepolymer is dissolved into cyclohexanone solvent and 1 equivalent of
DesmodurTM
3390 (triisocyanurate trimer of hexanediisocyanate) added as a crosslinker and
mixed.
The coating solution is 95% solids with a viscosity of 3000 centipoise. The
solution
can be flow-coated onto any bisphenol A polycarbonate such as Lexan and cured
in
an oven at 250 F (121 C) for 4 hours. The coating thickness can range from 2
to 5
mils thick and is elastomeric.
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[00544] The number and
thickness of the layers can vary as desired. For
example the thickness of a single layer can range from about 0.1 mm to about
60 cm,
or about 2 mm to about 60 cm, or about 0.3 cm to about 2.5 cm. The number of
layers
can range from 2 to 10, or 2 to 4, as desired. The overall thickness of the
multilayer
article or laminate can range from about 2 mm to about 15 cm or more, or about
2 mm
to about 5 cm. For ballistics applications, the overall thickness of the
polyurethane or
poly(ureaurethane) of the present invention can range from about 2 mm to about
15
cm or more, or about 2 mm to about 5 cm. Also, for ballistics applications
suitable
substrates for layering with the polyurethane(s) and/or poly(ureaurethane)s of
the
present invention include polyesters, polycarbonates, or polyether
thermoplastic
elastomers, for example. The layer(s) of polyurethane or poly(ureaurethane) of
the
present invention can be positioned on the outside of the laminate (facing the
potential
ballistic impact), on the inside of the laminate, or elsewhere in between.
Groups A-R
[00545] In some non-limiting embodiments, polyurethanes and
poly(ureaurethane)s of the present invention can have a hard segment content
of
about 10 to about 100 weight percent, or about 20 to about 80 weight percent,
or about
30 to about 75 weight percent. Hard segment calculation is discussed in detail
above.
[00546] In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of the present invention generally have a urethane content
(Wu)
of about 20 to about 40 weight percent, or about 21 to about 36 weight
percent, or
about 30 to about 40 weight percent. The urethane content is the percentage by
weight of the urethane linkages present in the polymer and can be calculated
by
determining the total number of equivalents, and from this the total weight of
all
reactants, and dividing the total weight of the urethane linkages obtainable
from these
reactants by the total weight of the reactants themselves. The following
example will
further explain the calculation. In Example I,
Formulation 1 which follows, a
polyurethane article according to the invention was prepared by reacting 0.7
equivalents of 1,4-butanediol, 0.3 equivalents of trimethylolpropane and one
equivalent
of 4,4'-methylene-bis-(cyclohexyl isocyanate) (DESMODURTm \/\/). The
equivalent
weight of the 1,4-butanediol is 45, the equivalent weight of the
trimethylolpropane is
44.7 (corrected for impurities) and the equivalent weight of the DESMODURTm W
is
131.2. Therefore, the actual weight of ingredients used is 31.54 parts by
weight of 1,4-
butanediol, 13.2 parts by weight of trimethylolpropane and 131.2 parts by
weight of
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DESMODURTm W or a total reactant weight of 175.9 parts by weight. One
equivalent
of DESMODURTm W will yield one equivalent of urethane linkage. The equivalent
weight of a urethane linkage is 59 so that the total weight of the urethane
linkages
determined by multiplying the equivalent weight by the number of equivalents
would
also be 59. Thus, the total weight of the urethane linkage, 59, divided by the
total
weight of the reactants, 175.9, multiplied by 100 to convert to percentages
would give
a percentage by weight of urethane linkage of 33.49 percent by weight.
1005471 In an
analogous manner, the percentage by weight of cyclic structures
(We) (such as for example cyclohexyl) can be calculated. In Example I,
Formulation 1,
the only material contributing cyclohexyl moieties is the DESMODURTm W. One
equivalent of DESMODURTm W would yield one equivalent of cyclohexyl moiety
which
has an equivalent weight of 81. Thus, the total weight of cyclohexyl moiety
would be
equal to 81 and this divided by the total weight of reactants or 175.9 would
yield a We
of 46 percent. In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of the present invention can have a cyclic content of
about 10 to
about 80 weight percent, about 20 to about 70 weight percent, about 30 to
about 70
weight percent, or about 30 to about 60 weight percent.
[00548] In some non-
limiting embodiments, the resulting polyurethanes or
poly(ureaurethane)s of the present invention when cured can be solid, and
essentially
transparent. In some non-limiting embodiments, the polyurethane can be
partially
cured or fully cured such that essentially no further reaction occurs.
[00549] In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of the present invention generally have a number average
molecular weight, as estimated from inherent viscosity measurements, of at
least
about 20,000 grams/mole, or ranging from about 20,000 to about 1,000,000
grams/mole, or ranging from about 20,000 to about 800,000 grams/mole. The
polyurethanes and poly(ureaurethane)s of the present invention generally have
an
average molecular weight per crosslink of at least about 500 grams per mole,
in some
embodiments ranging from about 500 and about 15,000 grams/mole, or ranging
from
about 1800 and about 15,000 grams/mole. The
polyurethanes and
poly(ureaurethane)s of the present invention generally have a crosslink
density of at
least about 11,000 grams per mole.
[00550] In some non-
limiting embodiments, the polyurethane(s) and
poly(ureaurethane)s of the present invention when cured can have low density.
In
some non-limiting embodiments, the density can be from at least 0.9 to less
than 1.25
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grams/cm3, or from at least 1.0 to less than 1.45 grams/cm3, or from 1.08 to
1.37
grams/cm3, or from 1.08 to 1.13. In some non-limiting embodiments, the density
of
polyurethanes and poly(ureaurethane)s of the present invention can be less
than
LEXAN (density about 1.21 g/cm3) and conventional stretched acrylic (density
about
1.18 g/cm3). The density can be measured using a DensiTECH instrument
manufactured by Tech Pro, Incorporated. In some non-limiting embodiments, the
density is measured in accordance with ASTM D 792-00.
[00551] Also, some optically clear polyurethanes and poly(ureaurethane)s
upon
heating can exhibit a low temperature exotherm at about -70 C (differential
thermal
analysis can be determined using a du Pont 900 thermal analyzer), and about 11
C,
indicating that the polymers are generally amorphous.
[00552] In some non-limiting embodiments, softening points of about 65 C to
about 200 C, melting points of about 80 C to about 220 C, and decomposition
temperatures of about 280 C to about 330 C under nitrogen atmosphere are
typical.
[00553] The polyurethanes and poly(ureaurethane)s of the present invention
can be used to form articles having good impact resistance or flexibility,
high impact
strength, high tensile strength, resistance to heat distortion, good hardness,
high
Young's modulus, high K factor, good solvent resistance, good clarity or
transparency,
high light transmittance, low haze, good weatherability, good energy-
absorption, good
moisture stability, good ultraviolet light stability, and/or good ballistics
resistance.
[00554] Non-limiting examples of suitable methods and equipment for
measuring impact resistance and impact strength are discussed in detail above.
[00555] In some embodiments, the heat distortion temperature of cured
articles
of the invention can be at least about 190 F (88 C) or above about 200 F (93
C), as
determined according to ASTM-D-648.
[00556] Hardness of the polyurethanes and poly(ureaurethanes) can be
determined by the Shore hardness and accordingly, in some embodiments articles
of
the invention have a Shore D hardness at room temperature (25 C) using a Shore
D
durometer of at least about 75 or at least about 80.
[00557] Tensile strength at yield or break can be measured according to
ASTM-
D 638-03. In some non-limiting embodiments, the tensile strength at yield is
at least
about 6,800 lb/in2 (47 MPa) according to ASTM-D 638-03, or about 6,800 to
about
20,000 lb/in2 (about 47 to about 138 MPa), or about 12,000 to about 20,000
lb/in2
(about 83 to about 138 MPa).
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[00558] Young's
Modulus can be measured according to according to ASTM-D
638-03. In some non-limiting embodiments, the Young's Modulus is at least
about
215,000 lb/in2 (about 1482 MPa), or about 215,000 (about 1482 MPa) to about
600,000 lb/in2 (about 4137 MPa), or about 350,000 (about 2413 MPa) to about
600,000 lb/in2 (about 4137 MPa). For commercial airplane cabin window
applications,
when the cabin pressure is 10 psi (0.07 MPa) or more greater than the external
pressure, the cabin windows can deflect into the airstream, thereby increasing
noise
and decreasing fuel efficiency. Higher values of Young's Modulus indicate
increased
stiffness and less tendency for the window to deflect into the airstream. In
some non-
limiting embodiments for aircraft window applications, the values of Young's
Modulus
can be at least about 350,000 (about 2413 MPa). In typical ballistics
applications, the
outer plies are glass, which is hard enough to deform a bullet by spreading
the impact
stress over a large area before it penetrates the underlying plies. A
poly(ureaurethane) prepared according to Example A, Formulation 125 according
to
the present invention having a thickness of about 0.125 inches (0.3 cm)
flattened a 9
mm bullet fired at 1350 ft/sec (411 m/sec) from a distance of 20 feet (6.1 m).
Though
the ply broke into 2 cracked areas, it did not shatter over a large area like
glass, which
would provide greater visibility for an occupant to escape attack on a
vehicle.
[00559] K factor is a
measure of crack propagation. Crack propagation can be
measured according to U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993).
In some non-limiting embodiments, the polyurethanes and poly(ureaurethane)s of
the
present invention have a K-Factor crack propagation resistance of at least
about 1000
lb/in3/2 (1,098,800 N/m3/2), or about 1000 lb/in3/2 (1,098,800 N/m3/2) to
about 4000
lb/in3/2 (4,395,200 N/m3/2), or about 2000 lb/in3/2 (2,197,600 N/m3/2) to
about 4000
lb/i n312 (4,395,200 N/m3/2).
[00560] Compositions
suitable for use in automobile windshields meet the
standard requirement of minimum light transmission of 70 percent or 86.5
percent or
above (Illuminant A. Tungsten lamp 2,840 K.) and less than 2 percent haze
(ANSI
CODE Z-26.1, 1966, Test No. 18). The percent light transmission and percent
haze
can be measured by a Hunter Pivotable Sphere Haze Meter according to ASTM E903-
82.
[00561] The
polyurethanes and poly(ureaurethane)s of the present invention
can have outstanding weather characteristics as measured by UV light stability
and
hydrolytic stability. Fade-O-Meter0 exposure can be conducted according to
ASTM G-
25-70, Method A using a Fade-O-Meter, Type FDA-R, Serial No. F02951,
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CA 02647153 2012-12-19
manufactured by Atlas Electric Devices Co., Chicago, Illinois. The light
source can a
carbon arc lamp enclosed in a fused silica globe. The operating temperature of
the
Fade-O-Meter (black panel) can be 140 F (60 C) and the instrument operated
with no
water in the atomizing unit. Sample sizes are 21/2 inches by 1/8 inch (6.35 cm
by
15.24 cm by 0.32 cm). Weather-O-Meter exposure can be conducted according to
ASTM D-1499-64 using a Weather-O-Meter, Type DMC, Serial No. WO-1305. The
type of light source can be a twin carbon arc lamp enclosed in a fused silica
globe.
The operating black panel temperature can be 140 F (60 C). The spray of water
is
deionized water at a temperature of about 70 F (21 C). The number and type of
water
spray nozzles which are used are four No. 50 nozzles. Alternatively, the UV
resistance can be determined using QUV at 1000 hours according to ASTM G-53.
[00562] Abrasion
resistance can be measured using a Taber Abrader having a
CS-10F abrasion wheel with 500 grams of weight, for a sample size 3 inches by
3
inches by 1/8 inch (7.62 cm by 7.62 cm by 0.32 cm) according to ASTM D 1044-
99. In
some non-limiting embodiments, 100 cycles of Taber can result in 30% haze for
stretched acrylic and from 5% to 40%, or from 10% to 15% or less than about 5%
for
the polyurethanes and poly(ureaurethane)s of the present invention.
[00563] The
polyurethanes and poly(ureaurethane)s of the present invention
can have good craze resistance to solvents and acids. Craze resistance can be
measured according to U.S. Dept. of Defense MIL-PRF-25690B (January 29, 1993).
Non-limiting examples of solvents and acids for Stress Craze Testing include
methanol, isopropanol, ethylene glycol, propylene glycol, ethyl acetate,
acetone,
toluene, isobutyl acetate, Skydrol (hydraulic fluid), jet fuel such as JP-4,
and 75%
aqueous solution of sulfuric acid. In some non-limiting embodiments, uncoated
articles
prepared from the polyurethanes and poly(ureaurethane)s of the present
invention
have a stress craze resistance in organic solvent and 75% by weight aqueous
solution
of sulfuric acid of at least about 1000 psi (6.9 MPa) tensile stress, or about
1000 psi
(6.9 MPa) to about 4000 psi (27.6 MPa), or about 2000 psi (13.8 MPa) to about
4000
psi (27.6 MPa). In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of the present invention when uncoated can withstand 75%
sulfuric acid for up to thirty days or any organic solvent at between 1000 psi
(6.9 MPa)
and 4000 psi (27.6 MPa) membrane stress.
1005641 In some non-
limiting embodiments, the polyurethanes and
poly(ureaurethane)s of the present invention when polymerized can produce a
polymerizate having a refractive index of at least 1.55, or at least 1.56, or
at least 1.57,
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or at least 1.58, or at least 1.59, or at least 1.60, or at least 1.62, or at
least 1.65. In
other non-limiting embodiments, the poly(ureaurethane)s of the present
invention
when polymerized can produce a polymerizate having an Abbe number of at least
32,
or at least 35, or at least 38, or at least 39, or at least 40, or at least
44. The refractive
index and Abbe number can be determined by methods known in the art such as
American Standard Test Method (ASTM) Number D 542-00. Further, the refractive
index and Abbe number can be determined using various known instruments. In a
non-limiting embodiment of the present invention, the refractive index and
Abbe
number can be measured in accordance with ASTM D 542-00 with the following
exceptions: (i) test one to two samples/specimens instead of the minimum of
three
specimens specified in Section 7.3; and (ii) test the samples unconditioned
instead of
conditioning the samples/specimens prior to testing as specified in Section
8.1.
Further, in a non-limiting embodiment, an Atago, model DR-M2 Multi-Wavelength
Digital Abbe Refractometer can be used to measure the refractive index and
Abbe
number of the samples/specimens.
[00565] Solid articles that can be prepared using the polyurethanes or
poly(ureaurethanes) of the present invention include but are not limited to
optical
articles or lenses, photochromic articles or lenses, windows, transparencies,
such as
generally transparent windows, windshields, sidelights and backlights,
aircraft
transparencies, ballistic resistant articles, windmill components such as
blades, and
glazings.
1005661 In some non-limiting embodiments, the polymeric substrate material
including the coating composition applied thereto may be in the form of
optical
elements such as windows, piano and vision correcting ophthalmic lenses,
exterior
viewing surfaces of liquid crystal displays, cathode ray tubes e.g., video
display tubes
for televisions and computers, clear polymeric films, transparencies, e.g.,
windshields,
aircraft transparencies, plastic sheeting, etc.
1005671 The polyurethanes and poly(ureaurethane)s of the present invention
are
desirable for a wide variety of uses. They are particularly useful as glazing
materials
for aircraft safety glass windows. Besides aircraft glazing, the polyurethanes
and
poly(ureaurethane)s of the invention in sheet form can be used in
architectural
applications and can be tinted or made opaque by pigmenting if desired. In
such
applications, the polyurethanes and poly(ureaurethane)s of the invention can
be in
sheet form and may be used alone or laminated to other materials as discussed
above. The layers in the composite can have the same or different modulus
values, as
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desired. Also, in some embodiments the polyurethanes and poly(ureaurethane)s
of
the invention can be used for optical lenses since they can be optically
clear,
unaffected by ultraviolet light and humidity exposure and abrasion resistant.
[00568] In other non-limiting embodiments, the polyurethanes and
poly(ureaurethane)s of the present invention can be used as low thermal
expansion
substrates for deposition of conductive films for electrochromic applications,
microwave absorbing films or low resistance films. In other non-limiting
embodiments,
a stretched acrylic substrate can be coated with a cyanoethyl acrylate/acrylic
copolymer and further coated with the polyurethanes and poly(ureaurethane)s of
the
present invention.
[00569] The polyurethanes and poly(ureaurethane)s of the invention can be
used in sheet form and can vary in thickness from about 2 to 500 mils,
although
somewhat thinner and thicker sheets can be used, depending upon the
application.
For aircraft use, in some embodiments the thickness can vary between 1/8 inch
and
1/2 inch (0.32 cm to 1.27 cm).
[00570] In some embodiment, an automobile window can be prepared from a
thermoplastic polycarbonate resin, such as that sold under the trademark
LEXANe,
with the coating composition of the present invention applied as a weather
layer on the
outboard side of the window to increase the weatherability of the window.
Alternatively, an automobile window can be prepared as a glass/LEXANO
laminate,
with the glass as the outboard layer and the coating composition of the
present
invention applied as a layer on the inboard side of the laminate.
[00571] The coating composition of the present invention can be applied to
the
substrate surface using any known coating procedures. Desirably, the coating
composition is flow coated over the substrate surface by an automated flow-
coating
system in which the surface tension of the liquid pulls a coherent sheet of
liquid across
the substrate surface as the mechanical flow-coating device traverses across
the
substrate sheet. An automatic flow-coating device typically consists of an
articulating
arm that holds a nozzle connected to a pressure pot where the resin solution
is held.
The arm runs on a track above the sheet to be coated. The rate of flow of the
liquid is
adjusted using the pressure pot. The rate of traverse of the articulating arm
is set
using a potentiometer. The nozzle distance from the sheet is optimized and
kept
constant, via the articulating arm. This is particularly important for curved
sheets. The
thickness of the coating is determined by the initial viscosity of the resin
solution and
the rate of solvent evaporation. The evaporation rate is mainly controlled by
the
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solvent choice and the cubic feet/minute airflow in the ventilated coating
booth.
Alternatively, the coating compositions can be prepared and cast in an
appropriate
mold to form a desired structure, which can then be applied as a layer to a
suitable
substrate, such as through a lamination process, or may used as a monolithic
structure.
[00572] The coating composition generally may be applied to a substrate by
itself as a transparent or pigmented monocoat, or as the pigmented base coat
and/or
transparent topcoat in a color-plus-clear composite coating as known to those
skilled in
the art. In some embodiments, the coating can be applied before the isocyanate
and
hydroxyl groups are fully reacted, for example by spraying the isocyanate and
hydroxyl
components separately through a mixing nozzle to apply the coating to the
substrate.
Alternatively, the coating can be partially cured in an oven and then
subjected to a high
moisture environment, such as high humidity or water spray, to further react
and cure
the coating. If desired, the coating composition may contain additional
materials well
known in the art of formulated surface coatings, such as surfactants, flow
control
agents, thixotropic agents, fillers, antigassing agents, organic cosolvents,
catalysts,
and other customary auxiliaries. These materials can constitute up to 40
percent by
weight of the total weight of the coating composition.
[00573] As aforementioned, although the cured compositions can be formed
from liquid coating compositions, they also can be formed from coating
compositions
formulated as powder coating compositions.
[00574] In another non-limiting embodiment, the cured compositions of the
present invention also can be useful as decorative or protective coatings for
pigmented
plastic (elastomeric) substrates or mold-in-color ("MIC") plastic substrates.
In these
applications, the compositions can be applied directly to the plastic
substrate or
included in the molding matrix. Optionally, an adhesion promoter can first be
applied
directly to the plastic or elastomeric substrate and the composition applied
as a
topcoat thereover.
[00575] In another non-limiting embodiment, the compositions of the present
invention also can be useful as spalling shield layer, anti-lacerative coating
layer or
break-in resistant coating layer for glass or other substrates.
[00576] In a non-limiting embodiment, the polyurethane polymerizate of the
present invention can be used to prepare photochromic articles. In a further
embodiment, the polymerizate can be transparent to that portion of the
electromagnetic spectrum which activates the photochromic substance(s), i.e.,
that
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wavelength of ultraviolet (UV) light that produces the colored or open form of
the
photochromic substance and that portion of the visible spectrum that includes
the
absorption maximum wavelength of the photochromic substance in its UV
activated
form, i.e., the open form.
[00577] Photochromic
compounds exhibit a reversible change in color when
exposed to light radiation involving ultraviolet rays, such as the ultraviolet
radiation in
sunlight or the light of a mercury lamp. Various classes of photochromic
compounds
have been synthesized and suggested for use in applications in which a
sunlight-
induced reversible color change or darkening is desired. The most widely
described
classes of photochromic compounds are oxazines, pyrans and fulgides.
[00578] The general
mechanism responsible for the reversible change in color,
i.e., a change in the absorption spectrum in the visible range of light (400-
700 nm),
exhibited by different types of photochromic compounds has been described and
categorized. See John C. Crano, "Chromogenic Materials (Photochromic)", Kirk-
Othmer Encyclopedia of Chemical Technology, Fourth Edition, 1993, pp. 321-332.
The
general mechanism for the most common classes of photochromic compounds, e.g.,
indolino spiropyrans and indolino spirooxazines, involves an electrocyclic
mechanism.
When exposed to activating radiation, these compounds transform from a
colorless
closed ring compound into a colored open ring species. In contrast, the
colored form of
fulgide photochromic compounds is produced by an electrocyclic mechanism
involving
the transformation of a colorless open ring form into a colored closed ring
form.
[00579] A wide variety
of photochromic substances can be used in the present
invention. In a non-
limiting embodiment, organic photochromic compounds or
substances can be used. In alternate non-limiting embodiments, the
photochromic
substance can be incorporated, e.g., dissolved, dispersed or diffused into the
polymerizate, or applied as a coating thereto.
[00580] In a non-
limiting embodiment, the organic photochromic substance can
have an activated absorption maximum within the visible range of greater than
590
nanometers. In a further non-limiting embodiment, the activated absorption
maximum
within the visible range can be range from at least 590 to 700 nanometers.
These
materials can exhibit a blue, bluish-green, or bluish-purple color when
exposed to
ultraviolet light in an appropriate solvent or matrix. Non-limiting examples
of such
substances that are useful in the present invention include but are not
limited to
spiro(indoline)naphthoxazines and spiro(indoline)benzoxazines. These and other
suitable photochromic substances are described in U.S. Patents: 3,562,172;
- 134 -
CA 02647153 2012-12-19
3,578,602; 4,215,010; 4,342,668; 5,405,958; 4,637,698; 4,931,219; 4,816,584;
4,880,667; 4,818,096.
[00581] In another non-limiting embodiment, the organic photochromic
substances can have at least one absorption maximum within the visible range
ranging
from 400 and less than 500 nanometers. In a further non-limiting embodiment,
the
substance can have two absorption maxima within this visible range. These
materials
can exhibit a yellow-orange color when exposed to ultraviolet light in an
appropriate
solvent or matrix. Non-limiting examples of such materials can include certain
chromenes, such as but not limited to benzopyrans and naphthopyrans. Many of
such
chromenes are described in U.S. Patents 3,567,605; 4,826,977; 5,066,818;
4,826,977;
5,066,818; 5,466,398; 5,384,077; 5,238,931; and 5,274,132.
[00582] In another non-limiting embodiment, the photochromic substance can
have an absorption maximum within the visible range ranging from 400 to 500
nanometers and an absorption maximum within the visible range ranging from 500
to
700 nanometers. These materials can exhibit color(s) ranging from yellow/brown
to
purple/gray when exposed to ultraviolet light in an appropriate solvent or
matrix. Non-
limiting examples of these substances can include certain benzopyran compounds
having substituents at the 2-position of the pyran ring and a substituted or
unsubstituted heterocyclic ring, such as a benzothieno or benzofurano ring
fused to
the benzene portion of the benzopyran. Further non-limiting examples of such
materials are disclosed in U.S. Patent No. 5,429,774.
[00583] In some non-limiting embodiments, the photochromic substance for
use
in the present invention can include photochromic organo-metal dithizonates,
such as
but not limited to (arylazo)-thioformic arylhydrazidates, such as but not
limited to
mercury dithizonates which are described, for example, in U.S. Patent
3,361,706.
Fulgides and fulgimides, such as but not limited to 3-furyl and 3-thienyl
fulgides and
fulgimides which are described in U.S. Patent 4,931,220 at column 20, line 5
through
column 21, line 38, can be used in the present invention. .
[00584] In other non-limiting embodiments, the photochromic articles of the
present invention can include one photochromic substance or a mixture of more
than
one photochromic substances. In other non-limiting embodiments, various
mixtures of
photochromic substances can be used to attain activated colors such as a near
neutral
gray or brown.
[00585] The amount of photochromic substance employed can vary. In some
non-limiting embodiments, the amount of photochromic substance and the ratio
of
- 135 -
CA 02647153 2012-12-19
substances (for example, when mixtures are used) can be such that the
polymerizate
to which the substance is applied or in which it is incorporated exhibits a
desired
resultant color, e.g., a substantially neutral color such as shades of gray or
brown
when activated with unfiltered sunlight, i.e., as near a neutral color as
possible given
the colors of the activated photochromic substances. In some non-
limiting
embodiments, the amount of photochromic substance used can depend upon the
intensity of the color of the activated species and the ultimate color
desired.
[00586] In some non-
limiting embodiments, the photochromic substance can be
applied to or incorporated into the polymerizate by various methods known in
the art.
In a non-limiting embodiment, the photochromic substance can be dissolved or
dispersed within the polymerizate. In a other non-
limiting embodiments, the
photochromic substance can be imbibed into the polymerizate by methods known
in
the art. The term "imbibition" or "imbibe" includes permeation of the
photochromic
substance alone into the polymerizate, solvent assisted transfer absorption of
the
photochromic substance into a porous polymer, vapor phase transfer, and other
such
transfer mechanisms. In a non-limiting embodiment, the imbibing method can
include
coating the photochromic article with the photochromic substance; heating the
surface
of the photochromic article; and removing the residual coating from the
surface of the
photochromic article. In alternate non-limiting embodiments, the imbibition
process can
include immersing the polymerizate in a hot solution of the photochromic
substance or
by thermal transfer.
[00587] In some non-
limiting embodiments, the photochromic substance can be
a separate layer between adjacent layers of the polymerizate, e.g., as a part
of a
polymer film; or the photochromic substance can be applied as a coating or as
part of
a coating placed on the surface of the polymerizate.
[00588] The amount of
photochromic substance or composition containing the
same applied to or incorporated into the polymerizate can vary. In some non-
limiting
embodiments, the amount can be such that a photochromic effect discernible to
the
naked eye upon activation is produced. Such an amount can be described in
general
as a photochromic amount. In some non-limiting embodiments, the amount used
can
depend upon the intensity of color desired upon irradiation thereof and the
method
used to incorporate or apply the photochromic substance. In general, the more
photochromic substance applied or incorporated, the greater the color
intensity. In
some non-limiting embodiments, the amount of photochromic substance
incorporated
into or applied onto a photochromic optical polymerizate can be from 0.15 to
0.35
- 136 -
CA 02647153 2012-12-19
milligrams per square centimeter of surface to which the photochromic
substance is
incorporated or applied.
[00589] In another embodiment, the photochromic substance can be added to
the polyurethane prior to polymerizing and/or cast curing the material. In
this
embodiment, the photochromic substance used can be chosen such that it is
resistant
to potentially adverse interactions with, for example, the isocyanate present.
Such
adverse interactions can result in deactivation of the photochromic substance,
for
example, by trapping them in either an open or closed form.
[00590] Further non-limiting examples of suitable photochromic substances
for
use in the present invention can include photochromic pigments and organic
photochromic substances encapsulated in metal oxides such as those disclosed
in
U.S. Patents 4,166,043 and 4,367,170; organic photochromic substances
encapsulated in an organic polymerizate such as those disclosed in U.S. Patent
4,931,220.
[00591] The invention will be further described by reference to the
following
examples. Unless otherwise indicated, all parts and percentages are by weight.
EXAMPLES
[00592] The physical properties set forth below were measured as follows:
[00593] Light Transmittance (Y()) was measured according to ASTM E903-82;
[00594] Yellowness Index was measured according to ASTM D 1925-70;
[00595] Refractive index was measured on a multiple wavelength Abbe
Refractometer Model DR-M2 manufactured by ATAGO Co., Ltd.; the refractive
index
of liquids were measured in accordance with ASTM-D 1218; and the refractive
index of
solids were measured in accordance with ASTM-D 542;
[00596] Density (grams/cm3) of solids was measured in accordance with ASTM-
D 792-00;
[00597] Taber Abrasion (% haze) was measured for up to 100 cycles using a
Taber Abrader having a CS-10F abrasion wheel with 500 grams of weight, for a
sample size 3 inches by 3 inches by 1/8 inch (7.62 cm by 7.62 cm by 0.32 cm)
according to ASTM D 1044-99;
[00598] Bayer Abrasion (% haze) was measured for according to ASTM F 735-
94 (Reapproved 2001);
[00599] K-Factor crack propagation resistance was measured according to
U.S.
Dept. of Defense MIL-PRF-25690B (January 29, 1993).
- 137 -
CA 02647153 2012-12-19
[00600] Tensile strength at yield, percent elongation at yield, and Young's
Modulus were measured at about 25 C in accordance with ASTM-D 638-03;
[00601] Gardner Impact Strength was measured in accordance with ASTM-D
5420-04;
[00602] Dynatup Multiaxial Impact Strength was measured in accordance with
ASTM-D 3763-02;
[00603] Shore D Hardness was measured in accordance with a Shore D
durometer;
[00604] QUV-B testing was conducted for 1000 hours according to ASTM G-53;
[00605] Glass transition temperature (Tg) was measured using Dynamic
Mechanical Analysis; and
[00606] Linear Coefficient of Thermal Expansion was measured using a duPont
Thermomechanical analyzer (TMA) according to ASTM E 228-95.
[00607] The following abbreviations were used herein:
[00608] CHDM: 1,4-cyclohexane dimethanol;
[00609] Des N 3400: 60% hexamethylene diisocyanate dimer and 40%
hexamethylene diisocyanate trimer commercially available from Bayer;
[00610] Des W: 4,4'-methylene-bis-(cyclohexyl isocyanate) commercially
available from Bayer;
[00611] MDI: Methylene diphenyl 4,4'-diisocyanate;
[00612] Polycaprolactone diol: ToneTm 0210
polycaprolactone diol having
a molecular weight of 1000 g/mol commercially available from Solvay;
[00613] Polycarbonate diol 1: KM-10-1733 polycarbonate diol prepared from
hexanediol having a molecular weight of 1000 g/mol commercially available from
Stahl;
[00614] Polycarbonate diol 2: KM10-1667 polycarbonate diol prepared from
hexanediol having a molecular weight of 1000 g/mol commercially available from
Stahl;
[00615] TMDI: trimethylhexamethylene diisocyanate;
[00616] TMP: trimethylolpropane; and
1006171 TMXDIO: meta-tetramethylxylylene diisocyanate.
Example A
- 138 -
CA 02647153 2012-12-19
1006181 Polyurethanes and poly(ureaurethane)s of Formulations 1 through 133
were prepared from the components in amounts listed in Tables 1-18.
1006191 The polyurethanes (formulations not including water) were prepared
in
a glass kettle under nitrogen blanket with stirring. The polyisocyanate was
preheated
to a temperature of about 100 C before addition of the other components. The
mixture
was heated to a temperature of about 110 C over about 10 minutes and
maintained at
this temperature for about 30 minutes.
1006201 The poly(ureaurethane)s (formulations including water) also were
prepared in a glass kettle under nitrogen blanket with stirring. The
polyisocyanate was
preheated to a temperature of about 60 C.
1006211 For Formulations 123-127, 131, 132 and 133, the water was added to
the polyisocyanate and the temperature was maintained for about 30 minutes to
form
an isocyanate functional urea prepolymer. The other components were added and
the
mixture was heated to a temperature of about 90 C over about 10 minutes and
maintained at this temperature for about 30 minutes.
1006221 For Formulations 128-130, about 0.15 equivalents of
trimethylolpropane
was added to the polyisocyanate and the temperature was maintained for about
120
minutes to form an isocyanate functional ureaurethane prepolymer. The other
components were added and the mixture was heated to a temperature of about 110
C
over about 120 minutes and maintained at this temperature for about 4 hours.
1006231 Each of the polyurethane and poly(ureaurethane) mixtures was
degassed to remove carbon dioxide and cast into a 12"x13"x0.125" (30.5 cm x 33
cm x
0.3 cm) casting cell which had been preheated to a temperature of about 121 C.
The
filled cell was then cured in an oven fora period of about 48 hours at about
121 C.
- 139 -
Table 1
Formulation Polyisocyanate Branched Polyol Diol
Urethane Cyclic Molecular Hard
No. Type Equivalents Type Equivalents Type Equivalents
Content Content Weight per Segment
(wt.%) (wt.%) Crosslink Content
(g/mole)
(wt.%)
1 Des W 1.00 TMP 0.3 1,4-butanediol 0.7
33.49 _
45.98 1762 , 70.00
2 Des W 1.00 TMP 0.3 , 1,5-pentanediol ,
0.7 32.59 _
44.74 1810 71.00 ,
3 Des W 1.00 TMP 0.6 , 1,5-pentanediol ,
0.4 32.99 _
45.29 1788 , 41.00
4 Des W 1.00 _ TMP 0.3 1,6-hexanediol
, 0.7 31.73
_ _
_43.56 1860 71.00
Des W 1.00 TMP 0.3 Xylene glycol 0.35 30 41
_ =
76.00 1940 71.00 0
CHDM 0.35
6 Des W 1.00 TMP 0.3 . 1,5-pentanediol
0.35 31.37 58.00 1881 72.00 o
n.)
CHDM , 0.35
o,
7 Des W 1.00 TMP 0.3 1,6-hexanediol 0.35
30.97 57.34 1905 72.00 .o.
-4
1-,
CH DM 0.35
(xi
8 Des W 1.00 TMP 0.3 ..
1 8-octanediol
_ , 0.7 _
30.14 41.37 1958 73.00 w
9 Des W 1.00 TMP 0.3 1,10-decanediol
0.7 28.70 39.40 2056 74.00 n.)
Des W 1.00 TMP 0.3 _
1,8-octanediol 0.35 ,
29.40 40.36 2007 74.00 o
1-,
n.)
1,10-decanediol 0.35
1
11 Des W 1.00 TMP 0.8 _ .
CHDM 0.2
32.53 53.60 1814 22.00
n.)
1
12 Des W 1.00 TMP 0.3 _
CHDM 0.7
30.24 70.50 1951 73.00
13 Des W 1.00 TMP 0.8 1,5-pentanediol
0.2 33.26 45.67 , 1774 21.00 ko
14 Des W 1.00 TMP 0.3 1 ,7-heptaned io I
0.7 _ 30.91 42.44 1909 72.00
Des 1.00 TMP 0.3 _
1,9-nonanediol 0.7 _
29.40 40.36 2007 73.00
16 , Des W 1.00 TMP 0.3 1,12-dodecanediol
0.7 27.39 37.60 2154 75.60
17 Des W 1.00 TMP 0.6 1,10-decanediol , 0.4
_
30.59 42.00 1929 45.00
18 Des W 1.00 TMP 0.4 1,10-decanediol 0.4
_
29.75 .
40.84 1983 45.00
CHDM 0.2
19 Des W 1.00 TMP 0.3 1,10-decanediol
0.65 26.52 36.40 2225 63.00
Polycarbonate diol 1 0.05
TMDI 1.00 TMP 0.3 CHDM 0.7 34.91
47.92 1690 73.00
140
Table 2
Formulation Polyisocyanate Branched Polyol Diol
Urethane Cyclic Molecular Hard
No. Type Equivalents Type Equivalents Type Equivalents
Content Content Weight per Segment
(wt.%) (wt.%) Crosslink Content
(g/mole)
(wt.%)
21 Des W 1.00 TMP 0.3 1,4-butanediol 0.6 27.54 '
37.81 2142 49.00
Polycarbonate diol 1 0.1
22 Des W 1.00 TMP 0.3 lsopropylidene 0.7 25.79
35.41 2287 77.00
dicyclohexanol
_
23 Des W 1.00 TMP 0.4 . 1,10-decanediol 0.5 25.08
34.44 2352 46.00
Polycarbonate diol 1 0.1
o
24 Des W 1.00 TMP 0.3 1,10-decanediol 0.6 24.64
33.83 2395 46.00 o
Polycarbonate diol 1 0.1
n.)
25 Des W 1.00 TMP 0.3 1,4-butanediol 0.5 23.38
32.10 2523 ' 54.00 cn
.o.
Polycarbonate diol 1 0.2
-4
1-,
26 Des W 1.00 TMP 0.4 1,10-decanediol _
0.6 29.30 40.23 2013 65.00 (xi
w
27 Des W 0.5 TMP 0.3 1,10-decanediol 0.7 29.13
39.99 2025
MDI 0.5
n.)
0
28 Des W 1.00 TMP 0.3 1,12- 0.7 _
27.48
37.72 2147
n.)
1
cyclododecanediol
29 TMDI 1.00 TMP 0.2 CHDM 0.8 34.35
47.16 1718 73.00 n.)
1
30 1.00 TMP 0.3 Decanediol 0.45 29.34
40.28 2011
Xylene Glycol . 0.25
ko
31 Des W 0.3 TMP 0.3 1,10-decanediol 0.7 31.50
43.24 1873
TMDI 0.7
32 Des W 0.8 TMP 0.3 1,10-decanediol 0.5 27.62
37.92 2136 75.00
Bis(2-hydroxyethyl) 0.2
terephthalate
34 Des W 0.75 TMP 0.3 1,10-decanediol 0.7 28.91
39.69 2041 1
MDI 0.25
,
141
Table 3
Formulation Polyisocyanate Branched Polyol Diol
Urethane Cyclic Molecular Hard
No. Type Equivalents Type Equivalents Type Equivalents
Content Content Weight per Segment
(wt.%) (wt.%) Crosslink Content
(g/mole)
(wt.%)
35 Des W 0.85 TMP 0.3 1,10-decanediol 0.7 28.83
39.58 2047
MDI 0.15 .
36 TMXDI 8 1.00 TMP - 0.3 _
1 4-butanediol
. , 0.7 35.31
48.47 1671
37 Des W 1.00 TMP 0.3 1,10-decanediol 0.6 '
28.91 39.69 2041 75.00
1,4-cyclohexane 0.1
dimethanol
o
, .
38 Des W 1.00 TMP 0.3 1,10-decanediol 0.6 28.24
- 38.78 2089 74.00
Isopropylidene 0.10
0
n.)
Dicyclohexanol
39 Des W 1.00 TMP 0.3 1,8-octanediol 0.45 29.61
40.65 1993 70.00 .o.
-4
1,10-decanediol 0.25
1-,
40 Des W 1.00 TMP 0.35 1,10-decanediol 0.65 _
C.,,C.,,
29.00 39.81 2035 74.00 w
n.)
41 Des W 1.00 TMP 0.3 1,8-octanediol 0.4 29.50
40.50 2000 o
1-,
1,10-decanediol 0.30
n.)
1
42 Des W 1.00 TMP 0.3 1,8-octanediol 0.5 29.71
40.79 1986 73.00
n.)
'
1,10-decanediol 0.20
,
1-,
,
43 Des W 1.00 TMP 0.3 1,4-butanediol 0.1 28.12
38.61 2098 75.00 ko
1,12-dodecanediol 0.60
44 Des W 1.00 TMP 0.3 1,10-decanediol - 0.35
26.60 36.52 2218 76.00
Isopropylidene 0.35
dicyclohexanol
45 Des N 3400 1.00 1 10-decanediol
_ , 1. _
20.93 28.73 2820
46 Des N 3400 1.00 1,10-decanediol 0.8 21.15
29.04 2790
CHDM 0.20
47 Prepolymer 1.00 1,4-butanediol 0.75
13.29 18.24 4441
CHDM 0.25
142
Table 4
Formulation Polyisocyanate Branched Polyol Diol
Urethane Cyclic Molecular Hard
No. Type Equivalents Type Equivalents Type
Equivalents Content Content Weight per Segment
(wt.%) (wt.%) Crosslink Content
(glmole)
(wt.%)
,
48 Des W 1.00 TMP ' 0= .3 _
1,4-butanediol 0.35 -
33.04 45.35 1786 70.00
1,5-pentanediol 0.35
49 Des W 1.00 TMP . 0.3 1,5-pentanediol 0.6 32.22
44.23 1831 71.00
1,8-octanediol 0.10
50 Des W ' 1.00 TMP - 0= .3 1,5-pentanediol 0.6 31.97 _
43.89 1845 71.00
1,10-decanediol 0.10
(-)
51 Des W 1.00 TMP . 0.3 1,4-butanediol 0.2 32.84
45.09 1796 71.00 o
1,5-pentanediol 0.50
N.)
52 Des W 1.00 TMP 0.3 1,4-butanediol 0.5 33.23
45.62 1775 70.00 cn
.o.
-4
1,5-pentanediol 0.20
53 Des W 1.00 TMP 0.3 1,4-butanediol 0.6 32.99
45.29 1789 70.00 (xi
w
CHDM 0.10
n.)
54 Des W 1.00 TMP 0.3 1,5-pentanediol 0.6 32.23
44.25 1830 71.00 0
1-,
CHDM 0.10
n.)
1
55 Des W 1.00 ..
TMP 0.3 1,5-pentanediol 0.5 31.88
43.77 1850 71.00
CHDM 0.20
n.)
1
56 Des W 1.00 TMP 0.3 1,5-pentanediol 0.5 30.09
41.32 1960 71.00
ko
Bis(2-hydroxyethyl) 0.20
terephthalate
57 Des W 1.00 TMP 0.3 1,5-pentanediol 0.6 31.19
42.82 1892 73.00
lsopropylidene 0.10
dicyclohexanol
58 Des W 1.00 TMP 0.3 1,5-pentanediol 0.5 - 22.99
' 3= 1.56 2566 35.00
Polycarbonate diol 1 _ 0.2
59 Des W - 1.00 TMP 0.3 1,5-pentanediol 0.6 26.96
' 3= 7.01 2188 50.00
, Polycarbonate diol 1 0.1
60 Des W 1.00 TMP 0.3 1,5-pentanediol 0.3 26.25 _
36.04 2247 64.00
CHDM 0.3
_ Polycarbonate diol 1 0.10
61 Des W 1.00 TMP 0.4 1,5-pentanediol 0.1 22.55
30.95 2617 37.00
CHDM 0.3
Polycarbonate diol 1 0.20
143
Table 5
Formulation Polyisocyanate Branched Polyol Diol
Urethane Cyclic Molecular Hard
No. Type Equivalents Type Equivalents Type Equivalents
Content Content Weight per Segment
(wt.%) (wt.%) Crosslink Content
(g/mole)
(wt.%)
62 Des W 1.00 TMP 1.0 Polycarbonate diol 1 0.05
- 30.24 41.52 616 0.00
63 Des W 1.00 TMP 1.0 , Polycarbonate dial 1 _ 0.25
- 31.81 43.67 560 0.00
64 , Des W 1.00 TMP 0.9
Polycarbonate dial 1 _ 0.1 _7 27.53 37.80 716 0.00
65 Des W 1.00 . TMP 1.0
Polycarbonate dial 1 0.0132.82 45.06 543 0.00
66 Des W 1.00 _ TMP 1.00
_
33.54 46.05 1759 0.00
. _
67 Des W 1.00 TMP 0.35 1,5-pentanediol _
0.65 32.66 44.83 1562 66.00
68 Des W 1.00 TMP 0.40 1,5-pentanediol 0.6
32.72 44.93 1363 61.00 o
69 Des W 1.00 , TMP 0.70 1,5-pentanediol
0.3 , 33.13 45.48 770 31.00
70 Des W 1.00 TMP 0.651,5-pentanediol 0.35 33.06
45.39 1785 36.00 o
n.)
71 Des W 1.00 TMP 0.55 _
1,5-pentanediol 0.45 32.92
45.20 1792 46.00 a,
.o.
72 Des W 1.00 TMP 0.50 1,5-pentanediol 0.5
32.86 45.11 1796 51.00 -4
1-,
73 Des W 1.00 TMP 0.45 1,5-pentanediol _
0.55 32.79 45.02 1799 56.00 ul
74 Des W 1.00 TMP 0.70 1,10-decanediol 0.3
31.28 42.94 1886 35.00 w
75 Des W 1.00 TMP 0.65 _ 1,10-decanediol 0.35
30.93 42.47 1907 n.)
0
76 Des W 1.00 TMP 0.55 1,10-decanediol 0.45
30.26 41.54 1950 51.00
n.)
i
77 Des W 1.00 TMP 0.50 1,10-decanediol 0.5 _
29.93 41.10 1971 55.00
78 Des W 1.00 TMP 0.45 1,10-decanediol 0.55
30.26 41.54 1950
n.)
i
79 Des W 1.00 TMP 0.25 1,10-decanediol 0.75
28.41 39.00 2077 79.00
80 Des W 1.00 TMP 0.20 1,10-decanediol 0.8
28.12 38.60 2098 83.00 ko
81 Des W 1.00 TMP 0.15 1,10-decanediol _
0.85 , 27.84 38.22 2119 88.00
82 Des W 1.00 TMP 0.10 1,10-decanediol _ 0.9
27.56 37.84 2141 61.00
83 Prepolymer 1.00 1,4-butanediol 1.00
20.12 27.62 2933
84 Prepolymer 1.00 1,4-butanediol 0.75
19.66 27.00 3001
CHDM 0.25
85 Des W 0.41 PEG 0.03 1,4-butanediol 0.3565
56.78 77.95 1039
Polycaprolactone diol 0.003
PluronicTM 0.03
86 Des W 1.00 TMP 0.30 1,5-pentanediol 0.46
21.71 29.80 2718 31.00
Polycarbonate dial 1 0.24
87 Des W 1.00 TMP 0.30 1,5-pentanediol 0.47
22.02 30.22 2680
Polycarbonate dial 1 0.23
88 Des W 1.00 TMP 0.30 1,5-pentanediol 0.48
22.33 30.66 2642
Polycarbonate dial 1 0.22
144
Table 6
Formulation Polyisocyanate Branched Polyol Diol Urethane
Cyclic Molecular Wt. Hard Segmt
No. Type Equivalents Type Equivalents Type
Equivalents Content Content per Crosslink Content
_ (wt.%)
(wt.%) (g/mole) (wt.%)
89 Des W 1.00 TMP 0.30 1,5-pentanediol 0.49
22.65 31.10 2604
Polycarbonate diol 1 0.21
90 Des W 1.00 IMP 0.30 1,5-pentanediol 0.51
23.33 32.03 ' 2529
_ Polycarbonate diol 1 0.19
91 Des W 1.00 ' IMP 0.30 1,5-pentanediol
0.52 - 23.69 32.52 2491
Polycarbonate diol 1 0.18
.
92 Des W 1.00 -
IMP 0.30 1,5-pentanediol 0.53
24.05 33.02 2453
Polycarbonate diol 1 0.17
o
93 ' Des W 1.00 IMP 0.30 1,5-pentanediol
0.54 24.43 33.54 2415
Polycarbonate diol 1 0.16
o
n.)
94 Des W 1.00 IMP 0.30 1,5-pentanediol 0.55
24.82 34.07 2377 42.00 o,
o.
Polycarbonate diol 10.15
--3
95 Des W 1.00 IMP 0.3 1,5-pentanediol _
0.5 22.80
31.30 2020 1-,
(xi
Polycarbonate diol 2 0.2
w
96 Des W 1.00 IMP 0.3 1,5-pentanediol 0.65
29.43 40.41 2005 59.00 "
o
-
Polycarbonate diol 2 _ 0.05
97 Des W 1.00 IMP 0.3 1,4-butanediol 0.65 30.11
41.34 1959 n.)
1
1-,
Polycarbonate diol 2 0.05
n.)
1
98 Des W 1.00 IMP 0.3 1,5-pentanediol 0.6
26.83 36.84 _
2199
Polycarbonate diol 2 0.1
l0
99 Des W 1.00 IMP 0.3 1,4-butanediol 0.5 23.31
32.00 2532
Polycarbonate diol 1 0.2
100 Des W 1.00 - IMP 0.3 1,4-butanediol
0.6 - 27.49 37.73 2147
Polycarbonate diol 1 0.1
101 Des W 1.00 _
IMP 0.30 1,4-butanediol 0.46
21.97 30.16 2686
Polycarbonate diol 1 _ 0.24
102 Des W 1.00 ..
IMP 0.30 1,4-butanediol 0.47
22.29 30.60 2647
Polycarbonate diol 1 0.23
103 Des W 1.00 IMP 0.30 1,4-butanediol 0.48
22.62 31.05 2609
Polycarbonate diol 1 0.22
104 Des W ' 1.00 IMP 0.30 1,4-butanediol
0.49 22.96 31.52 2570
Polycarbonate diol 1 0.21
105 Des W 1.00 IMP 0.30 1,4-butanediol 0.51
23.67 32.49 2493
Polycarbonate diol 1 0.19
145
Table 7
Formulation Polylsocyanate Branched Polyol Dial
Urethane Cyclic Molecular Hard
No. Type Equivalents Type Equivalents Type Equivalents
Content Content Weight per Segment
(wt.%) (wt.%) Crosslink Content
.
(glmole) (wt.%)
106 Des W 1.00 TMP 0.30 1,4-butanediol 0.52 24.04
33.00 2455
Polycarbonate diol 1 , 0.18
107 Des W 1.00 TMP 0.30 1,4-butanediol 0.53 24.42
33.52 2416
Polycarbonate diol 1 0.17
108 Des W 1.00 TMP 0.30 1,4-butanediol - 0.54
24.81 34.07 2378
Polycarbonate diol 1 0.16
109 Des W 1.00 TMP 0.30 1,4-butanediol 0.55 25.22
34.63 2339 o
Polycarbonate diol 1 0.15
110 Des W 1.00 TMP 0.05 CHDM 0.95 29.22
40.11 2019 o
n.)
111 Des W 1.00 TMP 0.05 lsopropylidene bis 0.95
13.43 18.44 12900 96.00 o,
.o.
[(2-(2,6-dibromo-
-4
phenoxy)ethanol ,
1-,
C.),
112 Des W 1.00 TMP 0.05 CHDM 0.5 29.42
40.38 2006 96.00 w
Xylene glycol 0.45
"
113 Des W 1.00 TMP 0.05 1,8-octanediol 0.95 29.08
39.92 2029 o
1-,
114 Des W 1.00 TMP 0.05 1,10-decanediol , 0.95
27.29 37.47 2162 n.)
1
115 Des W 1.00 TMP - 0.05 CHDM 0.95 26.69
36.64 10965
_
n.)
'
Polycarbonate diol 1 0.05
116 Des W 1.00 TMP 0.05 1,4-butanediol 0.95 _
33.48
78.00 10570 95.00
ko
117 Des W 1.00 TMP 0.05 1,5-pentanediol 0.95 32.26
44.30 11000 96.00
118 Des W 1.00 . TMP 0.30_
Polycaprolactone diol 0.2 23.31
32.00 2531
. 1,5-pentanediol 0.5
119 Des W 1.00 TMP 0.30 Polycaprolactone diol 0.15
25.10 34.46 2351
1,5-pentanediol 0.55
120 Des W 1.00 TMP 0.30 Dibutyl-1,3- 0.7 28.03
38.48 2105 75.00
propanediol
_
121 Des W 1.00 TMP 0.30 Neopentyl glycol 0.7 32.58
44.74 1811 71.00
122 Des W 1.00 TMP 0.30 Ethylene glycol 0.7 35.50
- 48.80 . 1661 70.00
146
CA 02647153 2012-12-19
Table 8
Formulation Light Yellowness Refractive Density
No. Transmittance(%) Index Index (g/cm4)
' 1 91.84 0.44 1.524 1.1417
2 91.91 0.34 1.531 1.1307
3 91.9 0.33 1.531 1.1388
4 91.88 0.4 1.531 1.1209
91.58 0.66 1.544 1.1346
6 91.84 0.37 1.533 1.1261
7 91.87 0.34 1.531 1.1144
8 91.8 1.65 1.524 1.1051
9 91.93 0.5 1.527 1.0912
91.72 1.7 1.527 1.0929
1.524 1.0969
16 1.52 1.0685
17 1.525 1.1002
18 -
1.517 1.0976
19 1.521 1.0886
_1.517 1.0979
21 = 1.517 1.1327
23 1.523 1.1043
24 1.517 1.0971
1.521 1.1372
26 1.525 1.0876
29 1.512 1.0984
1.531 1.1049
31 1.508 1.072
32 1.527 1.1123
37 1.522 1.086
38 1.522 1.0831
39 1.524 1.0921
1.525 1.0846
41 1.522 _ 1.0866
42 1.524 1.0928
43 1.525 1.076
44 1.526 1.0796
58 1.145
147
Table 9
Formulation Taber Abrasion Bayer K-Factor Tensile
Elongation Gardner
No. Abrasion % Modulus at at Yield
Impact
Haze Yield (%)
Strength
# Cycles % Haze (113/in2)
(In-lbs)
1 100 28.5 29.45 1245.6 336000 41
427
2 60+ 30.8 31.48 1362.4 _ 367000
19/38 628
3 100 20.5 22.55 781.83 _ 350000
3.9/19 100
4 100 29 35.87 1313.6 . 311000 56
595
100 27.8 26.53 902.82 338000 4.7 168
o
6 100 24.7 28.75 1152.1 339000 32
214
7 100 _ 28.6 33.05 1230.1 327000 34
236 o
8 100+ 31.1 39.92 1522.3 287000 55
584 n.)
(3)
_
9 100+ 32.4 47.7 3564.8 251000 14
576 .o.
-.3
100+ 31 44.75 3104.1 258000 17
ol
60+ 32.7 42.17 2073 . 259000 16
512 w
16 60 45.9 45.5 _ 3621 238000 _
19 365 n.)
17 100 28.7 32.7 940 295000 8.4
158 o
1-,
18 26.4 34.68 1227 286000 14
220 "
1
19 33.9 45.9 4309 260000 14
595
n.)
25.1 42.88 1765 378000 4.3 553
1
21 28 40.77 3211 312000 14
536
ko
23 38 43.08 4628 265000 12
461
24 39.1 43.17 4869 251000 15
497
24.5 37.83 4528 246000 14 627
26 38.1 38.78 1415 _262000 19
179
28 42.6 834 327000 3
29 40.4 33.88 2351 369000 4.4
146
22.4 38.78 1150 274000 16 204
31 41.8 25.32 2252 216000 433
32 41.83 46.55 1852 278000 14
518
148
Table 10
Formulation Taber Abrasion Bayer K-Factor Tensile
Elongation Gardner
No. Abrasion % Modulus at at Yield
Impact
Haze Yield (%)
Strength
(Ib/in2)
(In-lbs)
# Cycles % Haze
38 45.82 41.72 1319 264000 15 614
39 46.58 38.47 1749 256000 18 632
40 45.78 44.52 1651 255000 22 531
41 45.02 41.7 1771 247000 16 356
42 36.23 41.12 1777 249000 18 581
0
43 43.12 40.85 4005 238000 15 598
44 41.88 35.67 997 279000 4.6 71
0
iv
48 295000 5.4 192
0,
0.
49 295000 6.1 327
1-,
50 284000 8.6 104
ol
51 290000 5.6 426
w
52 _
294000 8.3 71
iv
0
53 299000 5.3 112
iv
1
54 292000 5.3 111
55 292000 5.9 164
iv
1
56 314000 5.7 40
57 299000 5.1 70
ko
58 215000 20 365
59 4035 283000 10 299
60 1598 284000 18 379
61 260000 17 546
62 876 346000 3.2 24
63 737 334000 4.2 14
64 1119 349000 2.9 27
65 669 357000 2.8
66 638 368000 2.4 12
67 216
149
Table 11
Formulation Taber Abrasion Bayer K-Factor Tensile
Elongation Gardner Impact
No. Abrasion % Modulus at at Yield
Strength
# Cycles % Haze Haze Yield (INin2) (%)
(In-lbs)
68 203
69 133
70 80
71 56
72 106
73 136
74 40
75 38
0
76 63
77 _
64
0
iv
78 125
0,
Ø
79 333
-4
1-,
80 376
(xi
81 376
w
82 _
346
"
0
83 2235 _
1-,
n.)
I
84 2185
86 317
iv
1
87 328
88 451
kc
89 227000 15 472
90 244000 11 445
91 255000 21 411
92 263000 19 426
93 266000 9 443
94 270000 12 403
95 259000 13 406
96 280000 19 255
97 299000 5 290
98 272000 13 405
99 346
100 333
101 363
102 364
150
Table 12
Formulation Taber Abrasion Bayer K-Factor Tensile
Elongation Gardner Impact
No. Abrasion % Modulus at at Yield
Strength
# Cycles % Haze Haze Yield (%) (In-
lbs)
(113/in2)
103 367
104 367
105 360
106 404
107 362
108 371
109 327
110 97
113 334
114 552
(xi
118 82
=
0
1 5 1
CA 02 647153 2012-12-19
Table 13
Formulation Dynatup Shore D Glass Coefficient
No. Impact Hardness Transition of Thermal
Strength Temp. Expansion
(in/in)
,
1 17.6 79 126
2 , 24.28 88 119 81.91
3 4.04 88 140
4 25.4 86 117.1
8.6 88 156
6 15.2 86 132
7 27.2 86 129.9
8 31.5 82 106
9 38.4 80 99.1 94.65
35.5 81 102
24.8 80. 105
16 34.4 79 93
17 13.9 88 123.9
18 40.9 83 119
19 44.3 81 89.1
26.1 83 75.1 70.01
21 39.6 81 97
23 17.9 79 87 101.11
24 33.4 80 79.2 97.2
44.9 78 76.1 95.66
26 28.6 84 106
29 5.34 85 71.1 72.36
30.7 85 120.1
31 41 79 , 52.1 96.91
32 , 46.5 82 104
38 33.2 81 111.1
39 32.9 81 103.9
41.9 81 101.1
'
41 27.5 80
42 25.1 81
"
43 35.3 80 97
44 3.15 86
48 25.2 .
49 4.24
26.3
51 21.6
52 31.6
53 22.2
54 , 26.7
41.6
56 20..7
152
CA 02 647153 2012-12-19
Table 14
Formulation Dynatup Shore D Glass Coefficient
No. Impact Hardness Transition of Thermal
Strength Temp. Expansion
(inlin)
57 17.2
58 62.3 66
59 36.6
60 37.4
61 38.9
62 152
63 134
64 150
65 174
66 166
67 161
89 42.6
90 48.4
91 50.2
92 48
93 56.5
94 45.1
95 47.5
96 47.5
97 34.3
98 39.2
153
Table 15
Formulation Polyisocyanate Branched Polyol
Diol Urethane Cyclic Molecular Hard Water
No. Type Equivalents Type Equivalents Type Equivalents Content
Content Weight Segment (Equivalents)
(wt.%)
(wt.%) per Content
Crosslink
(wt.%)
(g/mole)
123 Des W 1.00 TMP 0.3 1,5-pentanediol 0.554
29.67 40.74 1988 0.19
Polycarbonate 0.57
diol 1
124 Des W 1.00 TMP 0.3 1,5-pentanediol 0.374
27.73 38.07 2128 0.22 o
Polycarbonate 0.11
diol 1
0
125 Des W 1.00 TMP 0.3 1,5-pentanediol _ 0.5
34.22 46.98 1724 0.20 n.)
cn
126 Des W 1.00 TMP 0.3 1,5-pentanediol 0.45
30.85 42.35 1913 0.20 .o.
--3
Polycarbonate 0.05
ol
diol 1
w
127 Des W 1.00 TMP 0.3 1,5-pentanediol 0.4
28.08 38.55 2101 0.20 n.)
Polycarbonate 0.1
o
1-,
diol 1
n.)
1
128 Des W 1.00 TMP 0.30 CHDM 0.6 31.25
42.91 1888 0.1
129 Des W 1.00 TMP 0.90 - 34.24
47.00 1723 0.1 n.)
1
130 Des W 1.00 TMP 0.30 _ CHDM _ 0.55 31.79
43.64 1856 0.15
ko
131 Des W 1.00 TMP 0.3 1,5-pentanediol 0.55
30.17 41.42 1956 0.10
Polycarbonate 0.05
diol 1
132 Des W 1.00 TMP 0.3 1,5-pentanediol 0.5
27.52 37.78 2144 0.10
Polycarbonate 0.1
diol 1
133 Des W 1.00 TMP 0.3 1,5-pentanediol 0.55
33.80 46.40 1746 0.15
154
CA 02647153 2012-12-19
Table 16
Formulation Light Yellow Refractive Density
No. Transmittance index Index (glcml
(0A)
125 1.119
126 1.125
127 1.133
128 1.113
129 1 128
_ =
130 1.113
131 1.127
132 1.129
155
Table 17
Formulation Taber Abrasion Bayer K-Factor Tensile
Elongation Gardner
No. Abrasion Modulus at at Yield
Impact
% Haze Yield (%) Strength
(ibtin2) (In-lbs)
# Cycles % Haze
o
._
125 355000 13 51
126 1113 305000 4 24
o
.
tv
127 1551 282000 12 244
cn
128
853 369000 16 56
0.
...3
-
129 686 441000 _ 7.5 8
Ul
130 766 389000 , 15 37
u.)
131290000 7.7 126
tv
. _
o
132 289000 19 328
1--`
133 289000 11 224
tv
1
1-"
Is.)
I
1--`
t 0
156
CA 02647153 2012-12-19
Table 18
Formulation Dynatup Shore D Glass Coefficient
No. Impact Hardness Transition of Thermal
Strength Temp. Expansion
(intin)
125 137
126 14.6 115
127 30 67
128 3.31 161
129 3
130 8.67 153
131 32.5
132
133 9.29
[00624] The above samples exhibited low yellowness, high light
transmittance,
high impact strength and good ballistic resistance.
[00625] A 6" x6" (15.2 cm x 15.2 cm) laminate of 2 inches (5.1 cm) of
molded
Formulation 2 below facing outward, laminated to a 1" (2.5 cm) ply of molded
Formulation 9 below, and 0.5" (1.3 cm) of molded Formulation 60 stopped or
deflected four consecutive AK-47, 7.62 mm x 39 mm shots from 150 feet (45.7
m).
Each layer was molded as described above. No glass ply was used in the
laminate.
The laminate was heated in an autoclave at about 300 F (149 C) for about 2
hours.
[00626] Samples of Polycast 84 aerospace stretched acrylic (commercially
available from Spartech of Clayton, Missouri) and samples of polymer of
Example A,
Formulation 2 (synthesized at 110 C and cured at 143 C as discussed above)
were
evaluated for physical properties as set forth in Table 19 below. The Sample
of
Example A, Formulation 2 had lower density, higher impact strength and
elongation,
and was tougher than the tested sample of stretched acrylic. LEXAN #8574K26
polycarbonate (commercially available from McMaster Carr Supply Co. of
Cleveland,
Ohio) and samples of polymer of Example A, Formulation 84 (synthesized at 110
C
and cured at 143 C as discussed above) were evaluated for physical properties
as
set forth in Table 20 below. The Example A, Formulation 84 had better solvent
resistance, UV resistance and higher impact strength than the tested sample of
LEXAN .
157
Table 19
Property Stretched Acrylic Sample of
Formulation 2 of Example A
Light Transmission 92 92
% Haze <1% <0.1%
Density 1.18 1.13
Solvent /75% aqueous sulfuric acid resistance 1000-4000 psi stress
o
K factor 2400 1500
0
Gardner Impact Test (in-lbs) 16 628
iv
0,
0.
High Speed Multiaxial Impact 3.6 (unprocessed) 26.5
..3
1-.
01
w
% Elongation (at break) 38%
iv
<5
0
1-.
iv
'
% Elongation (1000hrs QUV-B) <5 40%
iv
1
Tensile Strength 11,250 11,800
ko
Tensile Modulus 450,000 367,000
Glass Transition Temperature 205 247 F (119 C)
Heat Distortion Temp. shrinks above 180 F 235 F (113 C)
Abrasion Resistance: %Haze,100 cycles Taber Abrader 30 15
Refractive Index 1.49 1.519
Shore D Durometer 94 90
158
Table 20
Property Polycarbonate Sample of Formulation 84 of
Example A
Light Transmission 88 92
..
Density 1.2 1.08
Solvent Resistance Poor OH, H+, Acetone ' Good OH, H+, Acetone
-
Gardner Impact Mean Failure Energy 588 in-lb >640 in-lbs
(>72 J)
o
High Speed Multiaxial Impact 72 joules 105 Joules
0
% Haze, 100 cycles Taber Abrader 60% 15%
iv
0,
0.
Refractive Index 1.586 1.519
-4
1-,
(xi
Tensile Modulus 320,000 300,000
w
iv
Tensile Strength 8000psi 8500ps1
0
1-,
A, Elongation (at break) 100% 200%
iv
1
.
1-,
iv
% Elongation (1000hrs QUV-B) severe
degradation brittle-yellow 97% 1
1-,
Heat Distortion Temp. 275 F 220 F
ko
Glass Transition Temperature 305F 240F
Shore D Durometer 85 80
_
159
CA 02647153 2012-12-19
DMA Testing
[00627] A sample of Formulation 114 (prepared from 0.95 equivalents of 1,10-
decanediol, 0.05 equivalents of trimethylolpropane and 1.0 equivalents of 4,4'-
methylene-bis-(cyclohexyl isocyanate) (DESMODURTm W)) using Dynamic
Mechanical Analysis (DMA) for storage modulus, loss modulus and tan delta. The
DMA analysis was conducted on a solid, clamped sample (2" x 2" x 1/8") (5.1 cm
x
5.1 cm x 0.3 cm) vibrated at a frequency of 1 Hz over a wide temperature range
increased at a rate of 3 C/min. As shown in Fig. 16, the sample exhibited a
low
temperature transition in the loss modulus at about -70 C, which is unusual
for glass
polymers and indicates molecular torsional motion at this low temperature. A
second
transition is present at about 14 C. The glass transition temperature of this
polymer
is 71 C, which is a maximum in the tan delta graph. At this temperature, the
polymer
is most efficient at converting mechanical vibrations into heat, thus it is at
this
temperature that the polymer reaches a maximum in damping properties. The
storage modulus is the energy conserved by the polymer and can be related to
the
Young's Modulus or stiffness of the polymer.
Ballistics Testing
Example AA
[00628] A 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) thick sample of Formulation
2
from Example A above was cured at by heating at 290 F (143 C) for 48 hours.
Four
0.40 caliber bullets shot from 30 feet (9.1 m) at a velocity of 987 ft/sec
(300 m/sec)
ricocheted off the surface of the sample and the plastic did not crack. A
photograph
of a perspective view of the test sample is shown in Fig. 17.
Example AB
[00629] A 6"x6"x 3/8" (15.2 cm x 15.2 cm x 1 cm) formulation thick sample
of
Formulation 2 from Example A above was cured at by heating at 290 F (143 C)
for
48 hours. A 12 gauge shotgun shot from 20 feet (6.1 m) at a velocity of 1290
ft/sec
(393 m/sec) using heavy game lead shot pellets ricocheted off the surface of
the
sample and the plastic did not crack. A photograph of a front elevational view
of the
test sample is shown in Fig. 18.
160
CA 02647153 2012-12-19
Example AC
[00630] A 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) thick sample of Formulation
93 from Example A above was cured at by heating at 290 F (143 C) for 48 hours.
Three 9 mm bullets shot from 20 feet (6.1 m) at a velocity of 1350 ft/sec (411
m/sec)
stuck in the sample. A photograph of a front elevational view of the test
sample is
shown in Fig. 19.
Example AD
[00631] A 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) thick sample of Formulation
94 from Example A above was cured at by heating at 290 F (143 C) for 48 hours.
A
9 mm bullet shot from 20 feet (6.1 m) at am initial velocity of 1350 ft/sec
(411 m/sec)
stuck in the sample. Photographs of the test sample is shown in Figs. 20 and
21.
Fig. 20 is a perspective view of the sample showing the bullet embedded in the
sample surface. Fig. 21 is a side elevational view of the sample showing the
bullet
entrance into the sample.
Example AE
[00632] A 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) thick sample of Formulation
2
from Example A above was cured at by heating at 290 F (143 C) for 48 hours. A
6"x6"x1" thick sample of Formulation 9 from Example A above was cured at by
heating at 290 F (143 C) for 48 hours. A 6"x6"x0.5" (15.2 cm x 15.2 cm x 1.75
cm)
thick sample of Formulation 58 from Example A above was cured at by heating at
290 F (143 C) for 48 hours. A composite was prepared by assembling a 1" (2.5
cm)
thick layer of the sample of Formulation 2, a 1"(2.5 cm) thick layer of the
sample of
Formulation 9, and a 0.5" (1.25 cm) thick layer of the sample of Formulation
58 such
that the layer of Formulation 2 faced the rifle.
[00633] Four 7.62 x 39 mm bullets having a steel core were shot from an AK-
47 rifle from a distance of 30 yards (27.4 m) at an initial velocity of 2700
ft/sec (823
m/sec). The first bullet stopped in the middle layer of Formulation 9,
generally
parallel to the initial shot direction. The second through fourth bullets
stopped in the
far layer of Formulation 58, generally parallel to the initial shot direction.
Photographs of the test sample is shown in Figs. 22 and 23. Fig. 22 is a front
elevational view of a portion of the sample showing bullet entry points and
two bullets
embedded in the sample surface. Fig. 23 is a rear perspective view of the
sample
showing the two exiting bullets lodged in the Formulation 58 layer of the
sample.
161
CA 02647153 2012-12-19
Example AF
1006341 Samples prepared from Formulations 58 and 89-97 of Example A
above performed similarly, i.e., all "caught" bullets. A sample prepared from
Formulation 94 showed the least amount of sample penetration with about 1/8"
of the
back of the bullet protruding from the surface. No ductile bulge was observed
in the
back of sample prepared from Formulation 94. Penetration was greatly reduced
compared to samples prepared from Formulations 58 and 89-92
Example B
Comparative Non-limiting Example of Processing Temperature of 80 C vs. 110 C
1006351 Short chain diols (aliphatic diols having 4 to 8 carbon atoms as
discussed above) are typically immiscible in isocyanates due to the polarity
difference and surface tension difference between the two materials. It has
been
found that when the short chain diol and isocyanate are mixed at 80 C or less,
they
take longer to become a clear solution than at 110 C or higher. Although the
solutions may both appear clear, it has been found that there is an
inhomogeneity
that manifests itself in cured articles as much lower impact strengths than
when the
solutions are made at or above 110 C. In addition, when casting or reaction
injection
molding into a glass mold, any cooling that occurs from pouring and exposure
to air,
or the mold temperature being below 100 C exacerbates the inhomogeneity
problem
as further cooling increases the inhomegeneity. If temperatures drop even
further,
the short chain diol and isocyanate will phase separate and appear as haze.
This
haze generally will not clear in an oven heated to 120 C to 140 C after
pouring into a
mold and heating for 24 to 48 hours. Higher variations in impact strength also
have
been observed as the processing temperatures drop below 100 C. Above 110 C,
the initial Gardner impact strengths for polymers of this invention are higher
initially,
and show less variation in impact strengths from batch to batch when processed
above 110 C. The examples below illustrate the temperature effect.
Example B1
1006361 The following components 20.1 grams of 1,5 pentanediol, 7.5 grams
of trimethylolpropane and 72.45 grams of DESMODURTm W containing 20% trans-
trans isomer of 4,4'-methylene-bis-(cyclohexyl isocyanate) were charged into a
glass
kettle fitted with a thermometer and overhead stirrer. The charge was brought
up to
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a temperature of 110 C to 120 C while mixing and applying vacuum (2 mm mercury
(266 Pa)) to remove bubbles. The batch was mixed for 10 to 20 minutes after
reaching 110 C to 120 C.
[00637] The batch was cast into a heated glass mold that was preheated in
an
oven at 140 C. The polymer was cured for 48 hours at 140 C without catalyst.
After
curing, the mold was removed from the oven and allowed to cool to room
temperature. The plastic sheet was then removed from the glass mold and cut
into
2" x 2" x 1/8" (5.1 cm x 5.1 cm x 0.3 cm) samples for Gardner Impact testing.
The
initial Gardner impact strength averaged 260 in-lbs (30 J).
Example B2
[00638] The following components 20.1 grams of 1,5 pentanediol, 7.5 grams
of trimethylolpropane and 72.45 grams of DESMODURTm W containing 20% trans-
trans isomer of 4,4'-methylene-bis-(cyclohexyl isocyanate) were charged into a
glass
kettle fitted with a thermometer and overhead stirrer. The charge was brought
up to
a temperature of 80 C to 90 C while mixing and applying vacuum (2 mm mercury
(266 Pa)) to remove bubbles. The batch was mixed for 1 to 2 hours after
reaching
80 C to 90 C until the batch appeared clear.
[00639] The batch was cast into a heated glass mold that has been preheated
in an oven at 140 C. The polymer was cured for 48 hours at 140 C without
catalyst.
After curing, the mold was removed from the oven and allowed to cool to room
temperature. The plastic sheet was removed from the glass mold and cut into 2"
x 2"
x 1/8" (5.1 cm x 5.1 cm x 0.3 cm) samples for Gardner Impact testing. The
initial
Gardner impact strength averaged 62 in-lbs (7 J).
Example B3
[00640] The following components 17.9 grams of 1,4 butanediol, 7.4 grams of
trimethylolpropane and 74.47 grams of DESMODURTm W containing 20% trans-trans
isomer of 4,4'-methylene-bis-(cyclohexyl isocyanate) were charged into a glass
kettle
fitted with a thermometer and overhead stirrer. The charge was brought up to a
temperature of 110 C to 120 C while mixing and applying vacuum (2 mm mercury
(266 Pa)) to remove bubbles. The batch was mixed for 10 to 20 minutes after
reaching 110 C to 120 C.
[00641] The batch was cast into a heated glass mold that has been preheated
in an oven at 140 C. The polymer was cured for 48 hours at 140 C without
catalyst.
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After curing, the mold was removed from the oven and allowed to cool to room
temperature. The plastic sheet was removed from the glass mold and cut into 2"
x 2"
x 1/8" (5.1 cm x 5.1 cm x 0.3 cm) samples for Gardner Impact testing. The
initial
Gardner impact strength averaged 180 in-lbs (21 J).
Example B4
[00642] The following components 17.9 grams of 1,4 butanediol, 7.4 grams of
trimethylolpropane and 74.47 grams of DESMODURTm W containing 20% trans-trans
isomer of 4,4'-methylene-bis-(cyclohexyl isocyanate) were charged into a glass
kettle
fitted with a thermometer and overhead stirrer. The charge was brought up to a
temperature of 80 C to 90 C while mixing and applying vacuum (2 mm mercury
(266
Pa)) to remove bubbles. The batch was mixed for 1 hour to 2 hours after
reaching
80 C to 90 C until clear.
[00643] The batch was cast into a heated glass mold that has been preheated
in an oven at 140 C. The polymer was cured for 48 hours at 140 C without
catalyst.
After curing, the mold was removed from the oven and allowed to cool to room
temperature. The plastic sheet was removed from the glass mold and cut into 2"
x 2"
x 1/8" (5.1 cm x 5.1 cm x 0.3 cm) samples for Gardner Impact testing. The
initial
Gardner impact strength averaged 10- 15 in-lbs (1 J ¨ 1.5 J).
Example C
[00644] To estimate the overall percentage of aligned crystalline domains
in
samples of polyurethanes according to the present invention, samples of
Formulation
No. 2 (0.7 equivalents of 1,5-pentanediol (PDO), 0.3 equivalents of
trimethylolpropane (TMP) and 1 equivalent of 4,4'-methylene-bis-(cyclohexyl
isocyanate) (DESMODURTm W)) and Formulation No. 136 (0.95 equivalents of PDO,
0.05 equivalents of TMP and 1 equivalent of 4,4'-methylene-bis-(cyclohexyl
isocyanate) (DESMODURTm VV)) were tested using Differential Scanning
Calorimetry
(DSC) at 2 C/min and Thermogravimetric Analysis (TGA).
[00645] Each sample was prepared by mixing all components in the respective
formulation at about 110 C for about 30 minutes, degassed under vacuum for
about
to about 10 minutes, then casting in a glass mold heated to about 200 F (93 C)
for
about 48 hours and cooled to room temperature (25 C) and released from the
mold.
The sample of Formulation No. 2 was aged at about 25 C for about seven months.
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[00646] The sample of Formulation No. 136 (aged at about 25 C for about two
weeks) was used as control sample, and its percentage of aligned crystalline
domains was used as a reference for 100% crystallinity. With respect to the
100%
crystallinity of the sample of Formulation No. 136, the percentage of aligned
crystalline domains in Formulation No. 2 was calculated to be 42%. An
endothermic
peak at around ¨260 C was found for both samples and attributed to the melting
of
their ordered domains. The DSC data for each of the samples of Formulation
Nos. 2
and 136 are presented in Table 21 below and in Figs. 24 and 25, respectively.
Thermogravimetric Analysis data (TGA) for a sample of Formulation 136 is
presented
in Fig. 26.
Table 21
Summary of DSC Test Results
Sample No. 136 2
Equivalents and 0.95 PDO + 0.05 TMP + 1 0.7 PDO + 0.3 TMP +
Components of Des W 1 Des W
Formulation
Tg ( C) 99
Peak Endotherm ( C) 260 260
Heat Capacity (J/g) 3.77 1.63
Estimated Crystalline 100 (Control) 42
Domain (%)
Example D: Ballistic Testing
Example Dl:
[00647] A polyurethane polymer according to the present invention was
prepared from the components listed below in Table 22:
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CA 02647153 2012-12-19
Table 22
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,10-
Monomer Name decanediol TMP Des W 205.30 300.00
OH #
Acid #
Equivalent Wt. 87 44.00 131.2
Equivalents
desired 0.7 0.3 1.0
Mass Monomer 60.90 13.20 131.20
Weight %
Monomer 29.66% 6.43% 63.91%
Monomer masses
for experiment 88.99 19.29 191.72
Weight % Hard
Segment 74.40
Weight %
Urethane 28.74
Molecular Weight
per Crosslink
(g/mole) (Me) 2053.00
[00648] The 1,10 decanediol, trimethylolpropane and DESMODURTm W were
preheated to 80 C and added to a glass kettle. Under nitrogen blanket and with
constant stirring, the mixture was heated to ¨115 C and allowed to
compatibilize.
Once clear, the mixture was degassed, and cast into a 12"x12"x0.125" (30.5 cm
x
30.5 cm 0.3 cm) casting cell preheated to 121 C. The filled cell was cured for
48
hours at 143 C.
[00649] This formulation in a 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm)
thickness
passed a 0.40 caliber pistol shot from 30 feet (9.1 m) and 987 ft/sec speed
with no
cracking. From 20 feet (6.1 m) the bullet was also stopped and no cracking was
observed. Passed multiple 9 mm, 1350 ft/sec (411 m/sec) shots from 20 feet
(6.1 m)
without cracking. The formulation also passed 3 consecutive 12 gauge shotgun
shots (1290 ft/sec) from 30 feet (9.1 m) in a 3/8" thickness (18" x 12 "x
3/8") (46 cm x
30 cm x 1 cm) using heavy game lead shot. In each test, the bullets ricocheted
off
the target.
Example D2:
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[00650] A polyurethane polymer according to the present invention was
prepared from the components listed below in Table 23:
Table 23
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,5-
Monomer PC- pentanedi
Name 1733 ol TMP Des W 239.04 300.00
OH #
Acid #
Equivalent
Wt. 440 52.08 44.00 131.2
Equivalents
desired 0.15 0.55 0.3 1.0
Mass
Monomer 66.00 28.64 13.20 131.20
Weight % 27.61 54.89
Monomer % 11.98% 5.52% cio
Monomer
masses for
experiment 82.83 35.95 16.57 164.66
Weight %
Hard
Segment 35.84
Weight %
Urethane , 24.68
Molecular
Weight per
Crosslink
(g/mole) (Me) 2390.4
[00651] The 1,5 pentanediol, PC-1733, and
trimethylolpropane and
DESMODURTm W preheated to 80 C were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to -105 C and
allowed to
compatibilize. Once clear, the mixture was degassed, and cast into a
12"x12"x0.125"
(30.5 cm x 30.5 cm 0.3 cm) casting cell preheated to 121 C. The filled cell
was
cured for 48 hours at 143 C.
[00652] This formulation passed multiple 9mm, 115grain, 1350ft/sec shots by
"catching" in bulk of the polymer in a 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm)
sample.
The bullet penetration was approximately 0.25" (0.6 cm) with no ductile bulge
in the
back of the sample. The same formulation 4"x4"x1" (10.1 cm x 10.1 cm x 2.5 cm)
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sample also passed multiple 0.40 caliber shots in which the bullet was not
caught nor
ricocheted. The bullet was sitting, slightly deformed, at the base of the
sample. In a
3/8" (1 cm) thickness, this formulation passed 3 12 gauge shotgun shots from
30 feet
(9.1 m). Most of the shot was embedded in the surface of the sample
Example D3:
[00653] A polyurethane polymer according to the present invention was
prepared from the components listed below in Table 24:
Table 24
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name butanediol TMP Des W 175.94 300.00
OH #
Acid #
Equivalent Wt. 45.06 44.00 131.2
Equivalents desired 0.7 0.3 1.0
Mass Monomer 31.54 13.20 131.20
Weight % Monomer 17.93% 7.50% 74.57%
Monomer masses
for experiment 53.78 22.51 223.71
Weight % Hard
Segment 70.13
Weight % Urethane 33.53
Molecular Weight
per Crosslink
(g/mole) (Me) 1759.42
[00654] The 1,4-butanediol, trimethylolpropane and DESMODURTm W
preheated to 80 C were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to -105 C and allowed to
compatibilize.
Once clear, the mixture was degassed, and cast into a 12"x12"x0.125" (30.5 cm
x
30.5 cm 0.3 cm) casting cell preheated to 121 C. The filled cell was cured for
48
hours at 143 C.
[00655] This formulation in a 6"x6"x 1" (15.2 cm x 15.2 cm x 2.5 cm) sample
passed multiple 0.40 caliber shots from 30 feet (9.1 m) with no cracking. The
speed
of the 0.40 caliber was 987 ft/sec (300 m). In 3/8" thickness at 60 ft (18.2
m), it
passed multiple 12 gauge shotgun impacts with heavy gauge shot at 1290 ft/sec
(393
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m/sec) muzzle velocity. At 20 ft (6.1 m) and 30 ft (9.1 m), this formulation
in 1" (2.5
cm) thickness broke when shot with a 9mm pistol, 115 grain bullet with a speed
of
1350 ft/sec (411 m/sec).
Example D4:
[00656] A polyurethane polymer according to the present invention was
prepared from the components listed below in Table 25:
Table 25
Desired
Polymer Batch
Solids Wt. (g) Size (g)
1,5-
Monomer Name pentanediol TMP Des W 180.85 300.00
OH #
Acid #
Equivalent Wt. 52.075 44.00 131.2
Equivalents
desired 0.7 0.3 1.0
Mass Monomer 36.45 13.20 131.20
Weight %
Monomer 20.16% 7.30% 72.55%
Monomer
masses for
experiment 60.47 21.90 217.64
Weight % Hard
Segment 70.94
Weight %
Urethane 32.62
Molecular
Weight per
Crosslink
(g/mole) (Mc) 1808.53
[00657] The 1,5-pentanediol, trimethylolpropane and DESMODURTm W
preheated to 80 C were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨115 C and allowed to
compatibilize.
Once clear, the mixture was degassed, and cast into a 12"x12"x0.125" (30.5 cm
x
30.5 cm 0.3 cm) casting cell preheated to 121 C. The filled cell was cured for
48
hours at 143 C.
[00658] This formulation in a 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) sample
passed a 0.40 caliber pistol shot from 30 feet (9.1 m) and 987 ft/sec (300 m)
speed
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with no cracking. From 20 feet (6.1 m) the bullet was also stopped but some
small
cracks were observed. Passed multiple 9 mm, 1350 ft/sec (411 m/sec) shots from
20
feet (6.1 m) without cracking. The formulation also passed 3 consecutive 12
gauge
shotgun shots (1290 ft/sec) (393 m/sec) from 30 feet (9.1 m) in a 3/8" (1 cm)
thickness using heavy game lead shot.
Example D5:
1006591 A polyurethane polymer according to the present invention was
prepared from the components listed below in Table 26:
Table 26
Desire
d
Batch
Polyme Size
Solids r Wt. (g) (g)
1,5-
KM10- pentanedi Des
Monomer Name 1733 ol TMP W 258.44 300.00
OH # - -
Acid # - - - -
Equivalent Wt. 440 52.075 44.00 131.2
Equivalents
desired 0.2 0.5 0.3 1.0
131.2
Mass Monomer 88.00 26.04 13.20 0
_
Weight % 50.77
Monomer 34.05% 10.07% 5.11% %
Monomer
masses for 152.3
experiment 102.15 30.22 15.32 0
Weight % Hard
Segment 44.20
Weight %
Urethane 22.83
Molecular Weight
per Crosslink
(g/mole) (Me) 2584.38
100660] The 1,5 pentanediol, KM10-1733 polycarbonate diol, and
trimethylolpropane and DESMODURTm W preheated to 80 C were added to a glass
kettle. Under nitrogen blanket and with constant stirring, the mixture was
heated to
¨105 C and allowed to compatibilize. Once clear, the mixture was degassed, and
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cast into a 12"x12"x0.125" (30.5 cm x 30.5 cm 0.3 cm) casting cell preheated
to
143 C. The filled cell was cured for 48 hours at 121 C.
[00661] This formulation passed multiple 9mm, 115grain, 1350ft/sec (393
m/sec) shots by "catching" in bulk of the polymer in a 6"x6"xl" (15.2 cm x
15.2 cm x
2.5 cm) sample. The bullet penetration was approximately 0.5" (1.2 cm) with a
slight
ductile bulge in the back of the sample. The same sample 4"x4"xl" (10.1 cm x
10.1
cm x 2.5 cm) also passed multiple 0.40 caliber shots in which the bullet was
not
caught nor ricocheted. It was sitting, slightly deformed at the base of the
sample. In
a 3/8" (1 cm) thickness this formulation passed 3 - 12 gauge shotgun shots
from 30
feet (9.1 m). Most of the shot was embedded in the surface of the sample.
1006621 All 9 mm shots were 115 grain, 1350 ft/sec (411 m/sec) muzzle
velocity shot from a Ruger 9 mm pistol. All 0.40 caliber shots were shot at
987 ft/sec
(300 m) muzzle velocity from a Smith & Wesson 0.40 caliber pistol. All 12
gauge
shotgun shots were shot using a Remington 12 gauge shotgun using lead shot,
heavy game load, at 1290 ft/sec (393 m/sec) muzzle velocity. Samples were shot
attached to a 12" thick wooden block using Velcro with no framing to hold the
sample. Shooting was conducted outdoors at temperatures ranging from about 60
F
(15 C) to about 80 F (27 C).
Example E
1006631 Samples prepared from Formulation 2 of Example A above were
prepared and tested for Gardner Impact Strength as in Example A above. Sample
El was prepared using a 35 weight percent trans, trans isomer of 4,4'-
methylene-bis-
(cyclohexyl isocyanate). Sample E2 was prepared using a 17 weight percent
trans,
trans isomer of 4,4'-methylene-bis-(cyclohexyl isocyanate). The Gardner Impact
Strength of Sample El was 150 in-lbs (17 J). The Gardner Impact Strength of
Sample E2 was 40 in-lbs (5 J). The Sample El prepared using a higher weight
percentage of trans, trans 4,4'-methylene-bis-(cyclohexyl isocyanate) had
higher
Gardner Impact Strength than Sample E2, which was prepared using a lower
weight
percentage of trans, trans 4,4'-methylene-bis-(cyclohexyl isocyanate).
Example F
1006641 Samples were prepared from Formulation 1 of Example 1 above,
further including 3 weight percent of CIBA TINUVINTm B75 liquid light
stabilizer
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CA 02647153 2012-12-19
system (commercially available from Ciba Specialty Chemicals)(which is a
mixture of
20 weight percent IRGANOXTM 1135, 40 weight percent of TINUVINTm 571 and 40
weight percent of TINUVINTm 765). The initial Gardner Impact Strength was 75
in-lbs
(9 J). After 1000 hours QUV-B, the Gardner Impact Strength was 75 in-lbs (9
J).
The initial tensile strength was 13,400 psi (92.4 MPa) and after 1000 hours
QUV-B
was 13,100 psi (90.3 MPa). The initial percent elongation was 40% and after
1000
hours QUV-B was 50%.
Example G
Elastoplastic Polyurethane Examples
Example G1
1006651 The following reactants 131.2 grams of DesmodurTM W, 13.41 grams
of trimethylolpropane, 26.015 grams of 1,5 pentanediol, and 81.712 grams Stahl
KM-
1733 1000 molecular weight polycarbonate diol based on hexanediol were mixed
together, heated to 80 C and degassed. Ten ppm of dibutyltindiacetate was
added
and mixed until the solution was homogeneous. The mixture was poured into a
glass
mold and cured for 48 hours at 290 F (143 C). After curing, the cell was
allowed to
cool to room temperature (25 C) and the polymer was released from the mold.
The
polymer had a Young's Modulus of 215,000 psi (about 1482 MPa). The weight %
urethane content was 23.4%. The molecular weight per crosslink was 2548
grams/mole. The weight % cyclic content was 32%.
1006661 An article of 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) thickness
prepared
from this polymer stopped a 9 mm, 125 grain, bullet shot an initial velocity
of 1350
ft/sec (411 m/sec) (from 20 feet (6.1 m) distance by trapping the bullet in
the polymer.
The back of the bullet penetrated approximately 1/8" (0.3 cm) into the sample
with a
very small raise on the backside.
Example G2
1006671 The following reactants 131.2 grams of DesmodurTM W, 13.41 grams
of trimethylolpropane, 28.096 grams of 1,5 pentanediol, and 65.370 grams Stahl
KM-
1733 1000 molecular weight polycarbonate diol based on hexanediol were mixed
together, heated to 80 C and degassed. Ten ppm of dibutyltindiacetate was
added
and mixed until the solution was homogeneous. The mixture was poured into a
glass
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mold and cured for 48 hours at 290 F (143 C). After curing, the cell was
allowed to
cool to room temperature (25 C) and the polymer was released from the mold.
The
polymer had a Young's Modulus of 215,000 psi (about 1482 MPa). The weight %
urethane content was 24.8%. The molecular weight per crosslink was 2404
grams/mole. The weight % cyclic content was 34%.
[00668] An article of 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) prepared from
this
polymer stopped a 9 mm, 125 grain, bullet shot an initial velocity of 1350
ft/sec (411
m/sec) from 20 feet (6.1 m) distance by trapping the bullet in the polymer.
Four/fifths
(4/5) of the length of the bullet penetrated the sample with the back of the
bullet
protruding out of the impacted surface approximately 1/8" (0.3 cm).
Example G3
[00669] The following reactants 131.2 grams of DesmodurTM W, 13.41 grams
of trimethylolpropane, 28.617grams of 1,5 pentanediol, and 61.284 grams Stahl
KM-
1733 1000 molecular weight polycarbonate diol based on hexanediol were mixed
together, heated to 80 C and degassed. Ten ppm of dibutyltindiacetate was
added
and mixed until the solution was homogeneous. The mixture was poured into a
glass
mold and cured for 48 hours at 290 F (143 C). After curing, the cell was
allowed to
cool to room temperature (25 C) and the polymer was released from the mold.
The
polymer had a Young's Modulus of 215,000 psi (about 1482 MPa). The weight %
urethane content was 25.15%. The molecular weight per crosslink was 2369
grams/mole. The weight % cyclic content was 34.53%.
[00670] An article of 6"x6"x1" (15.2 cm x 15.2 cm x 2.5 cm) prepared from
this
polymer stopped a 9 mm, 125 grain, bullet shot an initial velocity of 1350
ft/sec (411
m/sec) from 20 feet (6.1 m) distance by trapping the bullet. Four/fifths (4/5)
of the
length of the bullet penetrated the sample with the back of the bullet
protruding out of
the impacted surface approximately (0.3 cm).
Polv(urea urethane) Examples
Example G4
[00671] The following reactants 318.26 grams of DesmodurTM W and 0.84
grams of trimethylolpropane containing 0.5% of dibutyltindiacetate were
charged into
a glass kettle and heated and stirred at 75 C. Deionized water (4.37 grams)
was
added, mixed, and reacted to form polyurea hard segments within the
polyurethane
prepolymer. Carbon dioxide foam was removed under vacuum. The temperature
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CA 02647153 2012-12-19
was then increased to 80 C and reacted for 30 minutes. Outgassing was
performed
using 2 mm mercury vacuum and 63.42 grams of 1,5 pentanediol was added along
with 32.76 grams of trimethylolpropane. The mixture was stirred and vacuum
increased slowly. The exothermic temperature reached 95 C at which time the
mixture was poured into a 6"x6"x1/8" (15.2 cm x 15.2 cm x 0.3 cm) glass mold.
The
material was cured at 290 F (143 C) for 48 hours. The material was released
from
the mold at room temperature (25 C) yielding a clear, highly transparent
plastic.
Example G5
1006721 The following reactants 2.23 grams of trimethylolpropane was
reacted
with 76.133 grams of DesmodurTM W containing 10 ppm of dibutyltindiacetate at
80 C to formed a branched polyurethane terminated with isocyanate groups.
Water
(0.9 grams) was added to the batch after the temperature was lowered to 60 C,
and
reacted for 2 hours to form the polyurea portion of the polyurethane polyurea
prepolymer. The carbon dioxide was then removed with vacuum and 38 grams of
trimethylolpropane was added, mixed, degassed under vacuum and poured into a
glass mold as described above at 75 C. After curing for 48 hours at 290 F (143
C),
the plastic was removed from the mold at room temperature (25 C) yielding a
high
modulus, highly transparent plastic. The Young's Modulus was 441,000 psi
measured on an Instron testing machine at a 6"/minute crosshead speed.
Example G6
[00673] The following reactants 2.23 grams of trimethylolpropane was
reacted
with 131.2 grams of DesmodurTm W using 10 ppm of dibutyltindiacetate by weight
of
total batch to make a branched, isocyanate¨terminated polyurethane prepolymer.
Deionized water (1.34 grams) was added and reacted at 60 C. The carbon dioxide
was removed via vacuum degassing. The temperature was increased to 75 C and
39.66 grams of cyclohexanedimethanol was added as a chain extender. After
mixing
and degassing, the liquid was poured into a glass mold a described above and
cured
at 290 F (143 C) for 48 hours. Demolding was done at room temperature (25 C)
and yielded a high optical quality plastic sheet.
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Example H
Example H1
[00674] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name butanediol TMP Des W 175.94 300.00
OH #
Acid #
Equivalent Wt. 45.06 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 31.54 13.20 131.20
Weight % Monomer 17.93% 7.50% 74.57%
Monomer masses for
experiment 53.78 22.51 223.71
[00675] The 1,4-butanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
Once clear, the mixture was degassed and cast into a 12" x 12"x 0.125" (30 cm
x 30
cm x0.3 cm) casting cell preheated to 121 C. The casting was cured for 48
hours at
121 C and 6 hours at 150 C. The mean Gardner Impact Strength was 102 in-lbs
(12
J).
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CA 02647153 2012-12-19
Example H2
1006761 A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
Monomer 1,4-
Name butanediol TMP Des W 175.94 300.00
OH #
Acid #
Equivalent
Wt. 45.06 44.00 131.2
Equivalents
desired 0.7000 0.300 1.000
Mass
Monomer 31.54 13.20 131.20
Weight %
Monomer 17.93% 7.50% 74.57%
Monomer
masses for
experiment 53.78 22.51 223.71
Weight %
Hard
Segment 70.13
Weight %
Urethane 33.53
Mc 1759.42
1006771 The 1,4- butanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 110 in-lbs (13 J).
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Example H3
[00678] A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
1 ,4-
Monomer Name butanediol TMP Des W 175.94 300.00
OH #
Acid #
Equivalent Wt. 45.06 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 31.54 13.20 131.20
Weight % Monomer 17.93% 7.50% 74.57%
Monomer masses for
experiment 53.78 22.51 223.71
Weight % Hard
Segment 70.13
Weight % Urethane 33.53
Mc 1759.42
[00679] The 1,4-butanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 131 in-lbs (15 J).
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Example H4
1006801 A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
1,5-
Monomer Name pentanediol TMP Des W 180.85 300.00
OH #
Acid #
Equivalent Wt. 52.075 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 36.45 13.20 131.20
Weight % Monomer 20.16% 7.30% 72.55%
Monomer masses for
experiment 60.47 21.90 217.64
Weight % Hard
Segment 70.94
Weight % Urethane 32.62
Mc 1808.53
[006811 The 1,5-pentanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨115 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 135 in-lbs (15 J).
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Example H5
[00682] A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
1,5-
Monomer Name pentanediol TMP Des W 178.43 300.00
OH #
Acid #
Equivalent Wt. 52.075 44.00 131.2
Equivalents desired 0.4000 0.600 1.000
Mass Monomer 20.83 26.40 131.20
Weight % Monomer 11.67% 14.80% 73.53%
Monomer masses for
experiment 35.02 44.39 220.59
Weight % Hard
Segment 41.09
Weight % Urethane 33.07
Mc 892.15
[00683] The 1,5-pentanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨115 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 71 in-lbs (8 J).
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Example H6
[00684] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,5-
Monomer Name CHDM pentanediol TMP Des W 187.86 300.00
OH #
Acid #
Equivalent Wt. 72.11 52.075 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass Monomer 25.24 18.23 13.20 131.20
Weight %
Monomer 13.43% 9.70% 7.03% 69.84%
Monomer masses
for experiment 40.30 29.11 21.08 209.51
Weight % Hard
Segment 37.88
Weight %
Urethane 31.41
Mc 1878.65
[00685] The 1,5-pentanediol, CHDM, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 143 in-lbs (16 J).
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Example H7
[00686] A polyurethane was prepared from the following components:
Polymer Wt. Desired Batch
Solids (9) Size (g)
Monomer Name CHDM TMP Des W 194.88 352.00
OH #
Acid #
Equivalent Wt. 72.11 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 50.48 13.20 131.20
Weight % Monomer 25.90% 6.77% 67.32%
Monomer masses for
experiment 91.17 23.84 236.98
Weight % Hard Segment 73.03
Weight % Urethane 30.28
Mc 1948.77
[00687] The CHDM, trimethylolpropane, and DesmodurTM W (preheated to
80 C) were added to a glass kettle. Under nitrogen blanket and with constant
stirring, the mixture was heated to --105 C and allowed to compatibilize. The
mixture
was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x 0.3 cm)
casting
cell preheated to 121 C. The casting was cured for 48 hours at 121 C. The mean
Gardner Impact Strength was 63 in-lbs (7 J).
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Example H8
[00688] A polyurethane was prepared from the following components:
Polymer Wt.
Solids (g)
1,4-
Monomer Name CHDM butanediol TMP Des W 185.41
OH #
Acid #
Equivalent Wt. 72.11 45.06 44.00 131.2
Equivalents desired 0.3500 0.3500 0.300 1.000
Mass Monomer 25.24 15.77 13.20 131.20
Weight % Monomer 13.61% 8.51% 7.12% 70.76%
Monomer masses for
experiment 40.84 25.52 21.36 212.29
Weight % Hard Segment 38.38
Weight % Urethane 31.82
Mc 1854.10
[00689] The 1,4-butanediol, CHDM, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 47 in-lbs (5 J).
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Example H9
[00690] A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
1,6-
Monomer Name hexanediol TMP Des W 185.76 300.00
OH #
Acid #
Equivalent Wt. 59.09 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 41.36 13.20 131.20
Weight % Monomer 22.27% 7.11% 70.63%
Monomer masses for
experiment 66.80 21.32 211.88
Weight % Hard
Segment 71.71
Weight % Urethane 31.76
Mc 1857.63
[00691] The 1,6-hexanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated 10121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 130 in-lbs (15 J).
183
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Example H10
[00692] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,6- 1,4-
Monomer Name hexanediol butanediol TMP Des W 180.85 300.00
OH #
Acid #
Equivalent Wt. 59.09 45.06 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass Monomer 20.68 15.77 13.20 131.20
Weight '%
Monomer 11.44% 8.72% 7.30% 72.55%
Monomer
masses for
experiment 34.31 26.16 21.90 217.64
Weight % Hard
Segment 91.09
Weight %
Urethane 32.62
Mc 1808.53
[00693] The 1,6-hexanediol, 1,4-butanediol, trimethylolpropane, and
DesmodurTM W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨115 C and
allowed to
compatibilize. The mixture was degassed, and cast into a 12" x 12"x 0.125" (30
cm x
30 cm x 0.3 cm) casting cell preheated to 121 C. The casting was cured for 48
hours
at 121 C. The mean Gardner Impact Strength was 53 in-lbs (6 J).
184
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Example H11
[00694] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,6-
Monomer Name CHDM hexanediol TMP Des W 190.32 300.00
OH #
Acid #
Equivalent Wt. 72.11 59.09 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass Monomer 25.24 20.68 13.20 131.20
Weight %
Monomer 13.26% 10.87% 6.94% 68.94%
Monomer masses
for experiment 39.78 32.60 20.81 206.81
Weight % Hard
Segment 96.51
Weight %
Urethane 31.00
Mc 1903.20
[00695] The 1,6-hexanediol, CHDM, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨115 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 124 in-lbs (14 J).
185
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Example H12
[00696] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name cyclohexanediol TMP Des W 185.06 352.00
OH #
Acid #
Equivalent Wt. 58.08 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 40.66 13.20 131.20
Weight % Monomer 21.97% 7.13% 70.90%
Monomer masses
for experiment 77.33 25.11 249.56
Weight % Hard
Segment 71.60
Weight % Urethane 31.88
Mc 1850.56
[00697] The 1,4-cyclohexanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨95 C and allowed to
compatibilize.
Once clear, the mixture was degassed, and cast into a 6" x 6"x 0.25" (15 cm x
15 cm
x 0.3 cm) (30 cm x 30 cm x 0.3 cm) casting cell preheated to 121 C. The
casting
was cured for 48 hours at 121 C. The Gardner Impact Strength was 7 in-lbs (1
J).
186
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Example H13
[00698] A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
Ethylene
Monomer Name glycol TMP Des W 166.12 300.00
OH #
Acid #
Equivalent Wt. 31.035 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 21.72 13.20 131.20
Weight % Monomer 13.08% 7.95% 78.98%
Monomer masses for
experiment 39.23 23.84 236.93
Weight % Hard
Segment 68.36
Weight % Urethane 35.52
Mc 1661.25
[00699] The ethylene glycol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 4 in-lbs (4 J).
187
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Example H14
[00700] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name butanediol pentaerythritol Des W 172.95 -- 300.00
OH #
Acid #
Equivalent Wt. 45.06 34.04 131.2
Equivalents
desired 0.7000 0.300 1.000
Mass Monomer 31.54 10.21 131.20
Weight % Monomer 18.24% 5.90% 75.86%
Monomer masses
for experiment 54.71 17.71 227.58
Weight % Hard
Segment 71.34
Weight % Urethane 34.11
Mc 2306.04
[00701] The 1,4-butanediol, pentaerythritol, and DesmodurTM W (preheated to
80 C) were added to a glass kettle. Under nitrogen blanket and with constant
stirring, the mixture was heated to ¨150 C. The pentaerythritol never
dissolved.
188
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Example H15,
[00702] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name benzenedimethanol TMP Des W 192.76 300.00
OH #
Acid #
Equivalent Wt. 69.085 44.00 131.2
Equivalents
desired 0.7000 0.300 1.000
Mass Monomer 48.36 13.20 131.20
Weight %
Monomer 25.09% 6.85% 68.06%
Monomer masses
for experiment 75.26 20.54 204.19
95.81
Weight % Hard
Segment 72.73
Weight %
Urethane 30.61
Mc 1927.60
[00703] The 1,4-benzenedimethanol, trimethylolpropane, and DesmodurTm W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C and allowed to
compatibilize.
The mixture was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x
0.3
cm) casting cell preheated to 121 C. The casting was cured for 48 hours at 121
C.
The mean Gardner Impact Strength was 63 in-lbs (7 J).
189
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Example 1-118
1007041 A polyurethane was prepared from the following components:
Desired
Polymer Batch
Solids Wt. (g) Size (g)
Monomer 1,4-
Name CHDM benzenedimethanol TMP Des W 193.82 300.00
OH #
Acid #
Equivalent
Wt. 72.11 69.085 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass
Monomer 25.24 24.18 13.20 131.20
Weight %
Monomer 13.02% 12.48% 6.81% 67.69%
Monomer
masses for
experiment 39.07 37.43 20.43 203.08
Weight %
Hard Segment 98.38
Weight %
Urethane 30.44
Mc 1938.18
1007051 The 1,4-benzenedimethanol, CHDM, trimethylolpropane, and
DesmodurTm W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨115 C and
allowed to
compatibilize. The mixture was degassed, and cast into a 12" x 12"x 0.125" (30
cm x
30 cm x 0.3 cm) casting cell preheated to 121 C. The casting was cured for 48
hours
at 121 C. The mean Gardner Impact Strength was 75 in-lbs (9 J).
190
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Example H17
[007061 A polyurethane was prepared from the following components:
Desired
Polymer Batch
Solids Wt. (g) Size (g)
Monomer 1,4- 1,4-
Name benzenedimethanol butanediol TMP Des W 184.35 300.00
OH #
Acid #
Equivalent
Wt. 69.085 45.06 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass
Monomer , 24.18 15.77 13.20 131.20
Weight %
Monomer 13.12% 8.55% 7.16% 71.17%
Monomer
masses for
experiment 39.35 25.66 21.48 213.51
Weight %
Hard
Segment 93.16
Weight %
Urethane 32.00
Mc 1843.51
[007071 The 1,4-benzenedimethanol, 1,4-butanediol, trimethylolpropane, and
DesmodurTM W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨115 C and
allowed to
compatibilize. Once clear, the mixture was degassed, and cast into a 12" x
12"x
0.125" (30 cm x 30 cm x 0.3 cm) casting cell preheated to 121 C. The casting
was
cured for 48 hours at 121 C. The Gardner Impact Strength was 62 in-lbs (7 J).
191
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Example H18
1007081 A polyurethane was prepared from the following components:
Polymer
Solids Wt. (g)
1,4- 1,6-
Monomer Name benzenedimethanol hexanediol TMP Des W 189.26
OH #
Acid #
Equivalent Wt. 69.085 59.09 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass Monomer 24.18 20.68 13.20 131.20
Weight % Monomer 12.78% 10.93% 6.97% 69.32%
Monomer masses
for experiment 38.33 32.78 20.92 207.97
Weight % Hard
Segment 95.93
Weight % Urethane 31.17
Mc 1892.61
[00709] The 1,4-benzenedimethanol, 1,6-hexanediol, trimethylolpropane, and
DesmodurTM W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨115 C and
allowed to
compatibilize. Once clear, the mixture was degassed, and cast into a 12" x
12"x
0.125" (30 cm x 30 cm x 0.3 cm) casting cell preheated to 121 C. The casting
was
cured for 48 hours at 121 C. The Gardner Impact Strength was 64 in-lbs (7 J).
192
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Example I-119
[00710] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (9)
4,4'-trimethylene
Monomer Name dipiperidine TMP Des W 213.80 300.00
OH #
Acid #
Equivalent Wt. 99.14 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer , 69.40 13.20 131.20
Weight % Monomer 32.46% 6.17% 61.37%
Monomer masses
for experiment 97.38 18.52 184.10
Weight % Hard
Segment 75.42 =
Weight % Urethane 27.60
Mc 2137.98
[00711] The 4,4'-trimethylene dipiperidine, TMP and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. The initial temperature was
about
50 C, and when stirred jumped to about 60 C and gelled into a white mass.
193
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Example H20
[00712] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-bis(hydroxyethyl)
Monomer Name piperazine TMP Des W 205.38 300.00
OH #
Acid #
Equivalent Wt. 87.12 44.00 131.2
Equivalents
desired 0.7000 0.300 1.000
Mass Monomer 60.98 13.20 131.20
Weight %
Monomer 29.69% 6.43% 63.88%
Monomer masses
for experiment 89.08 19.28 191.64
Weight % Hard
Segment 74.41
Weight %
Urethane 28.73
Mc 2053.84
[00713] The 1,4-bis(hydroxyethyl) piperazine, trimethylolpropane, and
DesmodurTM W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨105 C, when the
viscosity raised to a point where it could no longer be stirred. The mixture
was not
clear and non-melted 1,4-bis(hydroxyethyl) piperazine was present in the
mixture.
194
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Example H21
[00714] A polyurethane was prepared from the following components:
Solids
N,N-bis(2-hydroxyethyl) 1,4-
Monomer Name oxamide butanediol TMP Des W
OH #
Acid #
Equivalent Wt. 88.08 45.06 44.00 131.2
Equivalents desired 0.3500 0.3500 0.300 1.000
Mass Monomer 30.83 15.77 13.20 131.20
Weight % Monomer 16.14% 8.26% 6.91% 68.69%
Monomer masses for
experiment 22.60 11.56 9.68 96.17
11.61 4.83 47.94
Weight % Hard Segment 40.18
Weight % Urethane 30.89
Mc 1909.99
[00715] The N,NI-bis(2-hydroxyethyl) oxamide, 1,4-butanediol,
trimethylolpropane, and DesmodUrTM W (preheated to 80 C) were added to a glass
kettle. Under nitrogen blanket and with constant stirring, the mixture was
heated to
¨105 C, when the viscosity raised to a point where it could no longer be
stirred. The
mixture was not clear and non-melted N,NI-bis(2-hydroxyethyl) oxamide was
present
in the mixture.
195
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Example H22
100716] A polyurethane was prepared from the following components:
Polymer Desired
Solids Wt. (g) Batch Size (g)
3,6-dithia-1,2-
Monomer Name octanediol TMP Des W 208.52 300.00
OH #
Acid #
Equivalent Wt. 91.6 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 64.12 13.20 131.20
Weight % Monomer 30.75% 6.33% 62.92%
Monomer masses
for experiment 92.25 18.99 188.76
Weight % Hard
Segment 74.79
Weight % Urethane 28.29
Mc 2085.20
1007171 The 3,6-dithia-1,2-octanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨105 C, when the viscosity raised
to the
point that it could no longer be stirred. The mixture was degassed, and cast
into a 6"
x 6"x 0.25" (15 cm x 15 cm x 0.3 cm) casting cell preheated to 121 C. The
casting
was cured for 48 hours at 121 C. The mean Gardner Impact Strength was 81 in-
lbs
(9J).
196
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Example H23
1007181 A polyurethane was prepared from the following components:
Polymer
Solids Wt. (g)
bis(4-(2-
3,6-dithia- hydroxyethoxy)-3,5-
Monomer 1,2- dibromophenyl)
Name octanediol sulfone CHDM TMP Des W 258.90
OH #
Acid #
Equivalent
Wt. 91.6 326.985 72.11 44.00 131.2
Equivalents
desired 0.2333 0.2333 0.2333 0.300 1.000
Mass
Monomer 21.37 76.30 16.83 13.20 131.20
Weight %
Monomer 8.26% 29.47% 6.50% 5.10% 50.68%
Monomer
masses for
experiment 24.77 88.41 19.50 15.30 152.03 300.00
Weight %
Hard
Segment 99.10
Weight %
Urethane 22.79
Mc 2588.96
1007191 The 3,6-dithia-1,2-octanediol, bis(4-(2-hydroxyethoxy)-3,5-
dibromophenyl) sulfone, CHDM, trimethylolpropane, and DesmodurTm W (preheated
to 80 C) were added to a glass kettle. Under nitrogen blanket and with
constant
stirring, the mixture was heated to ¨115 C and allowed to compatibilize. The
mixture
was degassed, and cast into a 12" x 12"x 0.125" (30 cm x 30 cm x 0.3 cm)
casting
cell preheated to 121 C. The casting was cured for 48 hours at 121 C.
197
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Example H24
1007201 A polyurethane polymer according to the present invention was
prepared from the components listed below:
Solids Polymer Wt. Desired Batch
(g) Size (g)
Monomer Name 2,2- TMP Des W 187.17 200.00
thiodiethanol
OH #
Acid #
Equivalent Wt. 61.10 44.00 131.2
Equivalents desired 0.7000 0.300 1.000
Mass Monomer 42.77 13.20 131.20
Weight % Monomer 22.85% 7.05% 70.10%
Monomer masses for 45.70 14.11 140.20
experiment
Weight % Hard Segment 71.92
Weight % Urethane 31.52
M. 1871.67
1007211 The 2,2-thiodiethanol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨95 C and allowed to
compatibilize.
Once clear, the mixture was degassed, and cast into a 6" x 6"x 0.25" (15 cm x
15 cm
x 0.3 cm) casting cell preheated to 121 C. The casting was cured for 48 hours
at
121 C. The Gardner Impact Strength was 5 in-lbs. (1 J) and the sample was
brittle.
198
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Example H25
[00722] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name thiodiethanol butanediol TMP Des W 181.56 300.00
OH #
Acid #
Equivalent Wt. 61.1 45.06 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass Monomer 21.39 15.77 13.20 131.20
Weight %
Monomer 11.78% 8.69% 7.27% 72.26%
Monomer
masses for
experiment 35.34 26.06 21.81 216.79
Weight % Hard
Segment 37.07
Weight %
Urethane 32.50
Mc 1815.56
[00723] The thiodiethanol, 1,4-butanediol, trimethylolpropane, and
DesmodurTM W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨105 C and
allowed to
compatibilize. The mixture was degassed, and cast into a 12" x 12"x 0.125" (30
cm x
30 cm x 0.3 cm) casting cell preheated to 121 C. The casting was cured for 48
hours
at 121 C. The mean Gardner Impact Strength was 39 in-lbs (4 J).
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Example H26
1007241 A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,6-
Monomer Name thiodiethanol hexanediol TMP Des W 186.47 300.00
OH #
Acid #
Equivalent Wt. 61.1 59.09 44.00 . 131.2
Equivalents
desired 0.3500 0.3500 0.300 1.000
Mass Monomer 21.39 20.68 13.20 131.20
Weight %
Monomer 11.47% 11.09% 7.08% 70.36%
Monomer
masses for
experiment 34.41 33.27 21.24 211.08
=
Weight % Hard
Segment 36.09
¨Weight %
Urethane 31.64
Mc 1864.67
1007251 The thiodiethanol, 1,6-hexanediol, trimethylolpropane, and
DesmodurTM W (preheated to 80 C) were added to a glass kettle. Under nitrogen
blanket and with constant stirring, the mixture was heated to ¨105 C and
allowed to
compatibilize. The mixture was degassed, and cast into a 12" x 12"x 0.125" (30
cm x
30 cm x 0.3 cm) casting cell preheated to 121 C. The casting was cured for 48
hours
at 121 C. The mean Gardner Impact Strength was 55 in-lbs (6 J).
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Example H27
100726] A polyurethane was prepared from the following components:
Polymer Desired Batch
Solids Wt. (g) Size (g)
1,4- Des N
Monomer Name butanediol 3400 Des W 182.80 300.00
OH #
Acid #
Equivalent Wt. 45.06 153.00 131.2
Equivalents desired 1.0000 0.300 0.700
Mass Monomer 45.06 45.90 91.84
Weight % Monomer 24.65% 25.11% 50.24%
Monomer masses for
experiment 73.95 75.33 150.72
Weight % Hard
Segment 96.42
Weight % Urethane 32.28
Mc 1828.00
[00727] The 1,4-butanediol, Des N 3400 and DesmodurTM W (preheated to
80 C) were added to a glass kettle. Under nitrogen blanket and with constant
stirring, the mixture was heated to ¨105 C. The mixture was degassed, and cast
into
a 6" x 6"x 0.25" (15 cm x 15 cm x 0.3 cm) casting cell preheated to 121 C. The
casting was cured for 48 hours at 121 C. The mean Gardner Impact Strength was
35 in-lbs (4 J).
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Example H28
[00728] A polyurethane was prepared from the following components:
Desired
Polymer Batch Size
Solids Wt. (g) (g)
1,4-
Monomer Name H20 butanediol TMP Des W 163.32 300.00
OH #
Acid #
Equivalent Wt. 9.01 45.06 44.00 131.2
Equivalents
desired 0.3500 0.3500 0.300 , 1.000
Mass Monomer 3.15 15.77 13.20 131.20
Weight %
Monomer 1.93% 9.66% 8.08% , 80.33%
Monomer masses
for experiment 5.79 28.97 24.25 240.99
Weight % Hard
Segment 79.41
Weight %
Urethane 36.12
Mc 1633.25
1007291 The 1,4-butanediol, TMP, DesmodurTM W (preheated to 80 C), and
deionized water were added to a glass kettle. Under nitrogen blanket and with
constant stirring, the mixture was heated to -105 C and allowed to
compatibilize.
After compatibilization, condensation (water) was observed on the sides of the
kettle.
Example H29
[00730] A polyurethane was prepared from the following components:
Component Equivalent Equivalents Weight (g) Weight (%)
Weight
TMP 44.7 0.05 2.2 1.3
1,4-butanediol 45 0.95 42.8 24.3
Des W 131 1.0 131 74.4
1007311 The 1,4-butanediol, TMP and DesmodurTM W (preheated to 80 C)
were added to a glass kettle. Under nitrogen blanket and with constant
stirring, the
mixture was heated to -110 C. The mixture was degassed, and cast into a 15" x
15"x 0.125" (38 cm x 38 cm x 0.3 cm) casting cell preheated to 121 C. The
casting
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was cured for 48 hours at 121 C. The mean Gardner Impact Strength was 300 in-
lbs
(35 J). The Wu was 33.5%, the Wc was 46% and the Mc was 10,569 g/mol.
Example H30
[00732] A polyurethane was prepared from the following components:
Component Equivalent Equivalents Weight (g) Weight (%)
Weight
TMP 44.7 0.05 2.2 1.2
1,5-pentanediol 52 0.95 49.5 27.1
Des W 131 1.0 131 71.7
[00733] The 1,5-pentanediol, TMP and DesmodurTM W (preheated to 80 C)
were added to a glass kettle. Under nitrogen blanket and with constant
stirring, the
mixture was heated to -110 C. The mixture was degassed, and cast into a 15" x
15"x 0.125" (38 cm x 38 cm x 0.3 cm) casting cell preheated to 121 C. The
casting
was cured for 48 hours at 121 C. The mean Gardner Impact Strength was 400 in-
lbs
(46 J). The Wu was 32.3%, the Wc was 44.3% and the Mc was 10,973 g/mol.
Example H31
1007341 A polyurethane was prepared from the following components:
Component Equivalent Equivalents Weight (g) Weight (%)
Weight
TMP 44.7 0.05 2.2 1.0
1,10-decanediol 87 0.95 82.8 38.3
Des W 131 1.0 131 60.6
[00735] The 1,10-decanediol, TMP and DesmodurTM W (preheated to 80 C)
were added to a glass kettle. Under nitrogen blanket and with constant
stirring, the
mixture was heated to -110 C. The mixture was degassed, and cast into a 15" x
15"x 0.125" (38 cm x 38 cm x 0.3 cm) casting cell preheated to 121 C. The
casting
was cured for 48 hours at 121 C. The mean Gardner Impact Strength was >640 in-
lbs (>74 J). The Wu was 27.3%, the IN, was 37.5% and the Mc was 12,974 g/mol.
The Dynatup Impact Strength was 77 Joules.
Example H32
[00736] A polyurethane was prepared from the following components:
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Component Equivalent Equivalents Weight (g) Weight (%)
Weight
TONE 210 406.4 0.2 81.3 32.3
1,5-pentanediol 52 0.5 26.0 10.3
TMP 44.7 0.3 13.4 5.3
Des W 131 1.0 131 52.0
1007371 The TONETm 210, 1,5-pentanediol, TMP and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to -110 C. The mixture was degassed,
and
cast into a 15" x 15"x 0.125" (38 cm x 38 cm x 0.3 cm) casting cell preheated
to
121 C. The casting was cured for 48 hours at 121 C. The Wu was 23.4%, the W,
was 32% and the Mc was 2542 g/mol.
Example H33
[00738] A polyurethane was prepared from the following components:
Component Equivalent Equivalents Weight (g) Weight (%)
Weight
TONE 210 406.4 0.15 61.0 26.1
1,5-pentanediol 52 0.55 28.6 12.2
TMP 44.7 0.3 13.4 5.7
Des W 131 1.0 131 56.0
[00739] The TONETm 210, 1,5-pentanediol, TMP and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to -110 C. The mixture was degassed,
and
cast into a 15" x 15"x 0.125" (38 cm x 38 cm x 0.3 cm) casting cell preheated
to
121 C. The casting was cured for 48 hours at 121 C. The Wu was 25.2%, the W,
was 34.6% and the Mc was 2342 g/mol.
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Example I
[00740] Samples of Formulations 1-10 of Example A, PlexiglasTM from
McMasterCarr, Poly 84 stretched acrylic and commercial grade LEXANO were
tested
for K-factor according to the following conditions:
Load cell: 2000 lbf
Humidity(%): 50
Temperature: 73 F (23 C)
Test Speed: 320 lb/min
Thickness: 0.120"
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Sample
Test# ID Width Thickness Crack Load Time K Factor
(in.) (in.) (in.) (lbs) (sec)
34 1A 2.138 0.123 0.575 345.800 345.800 1296.220
36 1B 2.144 0.122 0.600 318.400 318.400 1241.140
35 1C 2.135 0.128 0.700 294.200 294.200 1199.424
31 2A 1.995 0.123 0.750 304.400 304.400 1477.415
33 2B 1.990 0.131 0.650 322.100 322.100 1330.586
32 2C 1.965 0.132 0.750 278.700 278.700 1279.169
29 3A 1.986 0.125 0.475 216.400 216.400 777.079 ,
30 3B 1.972 0.130 0.425 228.200 228.200 746.028
1 3C 1.988 0.127 0.750 175.600 117.067 822.370
26 4A 2.017 0.125 0.600 327.500 327.500 1321.788
27 46 2.009 0.120 0.750 276.500 276.500 1359.195
28 4C 2.023 0.123 0.675 283.500 283.500 1259.891
24 5A 2.023 0.122 0.600 20.9.4 157.050 866.505
23 5B 2.020 0.120 0.750 179.900 107.940 874.598
25 5C 2.056 0.166 0.700 205.100 205.100 967.357
14 6A 2.053 0.124 0.650 291.000 218.250 1225.187
16 66 , 2.039 0.122 0.670
245.900 245.900 1086.512
15 6C 2.068 0.127 0.690 271.100 232.371 1144.531
12 7A 2.024 0.127 0.620 277.600 185.067 1125.576
13 76 2.034 0.130 0.750 288.300 192.200 1288.378
11 7C 2.019 0.128 0.750 278.700 101.345 1276.297
8A 2.006 0.124 0.960 238.400 158.933 1388.038
9 8B 2.021 0.124 0.800 284.600 87.569 1402.845
2 8C 2.009 0.118 0.750 355.400 266.550 1776.120
6 9A 2.003 0.118 0.520 1179.000 , 428.727 4681.823
8 9B 2.020 0.123 0.670 345.800 106.400 1525.675
7 9C 1.992 0.118 0.450 1220.000 395.676 4486.874
3 , 10A 2.010 0.116 0.750 782.300 586.725
3956.318
4 106 2.021 0.119 0.450 742.600 270.036 2655.849
5 10C 2.023 0.119 0.450 756.000 274.909 2700.237
21 11A 2.011 0.132 0.650 272.200 98.982 1106.454
22 116 2.006 0.130 0.650 220.700 115.148 910.576
11C 2.011 0.130 0.650 255.000 78.462 1048.797
19 12A 2.019 0.134 0.650 873.600 268.800 3470.984
17 , 126 2.021 0.132 0.680 798.900 290.509
3313.758
18 12C 2.023 0.133 0.710 863.400 313.964 3655.555
37 13A 2.036 0.125 1.500 1435.000 521.818 15960.663
38 13B 2.024 0.126 1.500 1401.000 262.688 15670.107
39 13C 2.024 0.133 1.500 1456.000 273.000 15489.381
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Example J
[00741] A polyurethane was prepared from the following components:
Desired
Batch Size
Solids Polymer Wt. (g) (g)
Monomer Name 1,5-pentanediol TMP Des W 2100.00
OH #
Acid #
Equivalent Wt. 52.075 44.00 131.2
Equivalents
desired 0.4000 0.600 1.000
Mass Monomer 20.83 26.40 131.20 178.43(sum)
Weight %
Monomer 11.67% 14.80% 73.53%
Monomer masses
for experiment 245.15 310.71 1544.13
Weight % Hard 0.4(131 + 52)/
Segment 41.09 178.43
Weight % 59g/eq./
Urethane 33.07 178.43g/eq.
178.43/
Mc 892.15 0.2 moles TMP
[00742] The 1,5-pentanediol, trimethylolpropane, and DesmodurTM W
(preheated to 80 C) were added to a glass kettle. Under nitrogen blanket and
with
constant stirring, the mixture was heated to ¨115 C and allowed to
compatibilize.
Once clear, the mixture was degassed, and cast into a 14" x 14"x 0.375"
casting cell
preheated to 121 C. A first set of samples was cured for 48 hours at 121 C. A
second set of samples was cured for 48 hours at 121 C and for 12 hours at 145
C.
Each set of samples was evaluated for stress craze resistance by immersion for
30
minutes in 75% aqueous solution of sulfuric acid. The second set of samples
passed
30 minutes at 4000 psi.
Example K
[00743] Trimethylolpropane (0.05 equivalents), 1,10-decanediol (0.95
equivalents) and DESMODURTm W (1.0 equivalents, preheated to 80 C) were added
to a glass kettle. Under nitrogen blanket and with constant stirring, the
mixture was
heated to 110 C and allowed to compatibilize. Once clear, the mixture was
degassed, and cast into a 12"x12"x0.125" casting cell preheated to 143 C. The
filled
cell was cured for 48 hours at 121 C. The Dynatup Multiaxial Impact Strength
was
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77 Joules, measured in accordance with ASTM-D 3763-02. The Dynatup Multiaxial
Impact Strength of a sample of Lexan was 72 Joules.
Example L
[00744] An isocyanate functional urethane prepolymer was prepared by
reacting using 0.3 equivalents of 1,5-pentanediol, 1.0 equivalent of
DesmodurTM W
and 10 ppm dibutyltin diacetate as reactants in a glass kettle under vacuum.
The
reaction temperature was maintained at 143 C for 10 hours and 0.4 equivalents
of
1,5-pentanediol and 0.3 equivalents of trimethylolpropane were added. After
about
30 minutes at 110 C, the mixture was cast between release coated glass molds
and
cured for 72 hours at 290 F (143 C). The mold was removed from the oven and
the
plastic released. The Gardner Impact strength was 256 in-lbs (29 J).
[00745] An isocyanate functional urethane prepolymer was prepared by
reacting using 0.5 equivalents of 1,5-pentanediol and 1.0 equivalent of
DesmodurTM
W and 10 ppm dibutyltin diacetate as reactants in a glass kettle under vacuum.
The
reaction temperature was maintained at 143 C for 10 hours and 0.2 equivalents
of
1,5-pentanediol and 0.3 equivalents of trimethylolpropane were added. After
about
30 minutes at 110 C, the mixture was cast between release coated glass molds
and
cured for 72 hours at 290 F (143 C). The mold was removed from the oven and
the
plastic released. The Gardner Impact strength was 256 in-lbs (29 J).
[00746] The sample prepared from an isocyanate functional urethane
prepolymer having a higher amount (0.5 equivalents) of 1,5-pentanediol had a
higher
Gardner Impact strength. While not intending to be bound by any theory, it is
believed that the miscibility between the components is improved by pre-
reacting a
portion of the short chain diol with the polyisocyanate.
Examples M
Example M1
[00747] An isocyanate functional prepolymer (NCO/OH ratio of 3.8) having an
equivalent weight of 327 grams/mole was prepared by reacting the following
components:
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Equivalent. Wt. Number of
Component Weight % equivalents
DESMODUR1 m W
4,4'-methylene-bis-(cyclohexyl 54.42
isocyanate) 131.2 0.42
DBT FASTCAT 4202
0.005
(dibutyl tin dilaurate)
PLURACOLTM E400NF
(polyethylene glycol) 5.095 200 0.03
PLURONIC1m L62D
(ethylene oxide/propylene oxide 33.97
block copolymer) 1180 0.03
TRIMETHYLOPROPANE 2.32 45 0.05
CAPATM 2077A
1.23
polycaprolactone polyol 375 0.003
IRGANOXTM 1010 0.49
CYASORBTM UV 5411 0.97
TINUVINTm 328 1.46
IRGANOXTM MD 1024 0.05
Total 100.000000
at a temperature of about 104 C for about 5 hours. All of the components were
mixed together, except the stabilizers which were dissolved after the
prepolymer was
reacted.
1007481 About 9 grams
of acrylamide was dissolved in about 45 grams of 1,4-
butanediol at a temperature of about 25 C and mixed with about 365 grams of
the
above prepolymer and about 0.1 weight percent of azobisisobutyronitrile (AIBN)
based on total solids. The mixture was cast into a glass mold and heated in an
oven
at a temperature of about 80 C for about 48 hours with constant stirring. A
clear
polymerizate was formed. A sample of the cured polymer was evaluated for light
transmittance and Gardner Impact Strength. The light transmittance of the
sample
was 91% and the Gardner Impact Strength was 150 in-lbs (17 J).
Example M2
1007491 A polyurethane
polymer according to the present invention was
prepared from the above isocyanate functional prepolymer,
cyclohexanedimethanol
(CHDM) and 1,4-butanediol as listed below:
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Desired
Polymer Batch
Solids Wt. (g) Size (g)
Monomer 1,4-
Name Prepolymer CHDM butanediol 417.53 200.00
OH #-
-
Acid #- - -
Equivalent
Wt. 365.71 72.11 45.06
Equivalents
desired 1.00 0.25 0.75
Mass
Monomer 365.71 18.03 33.80
Weight %
Monomer 87.59% 4.32% 8.09%
Monomer
masses
for
experiment 175.18 8.64 16.19
[00750] The prepolymer,
CHDM (preheated to 80 C) and 1,4-butanediol were
added to a glass kettle. Under nitrogen blanket and with constant stirring,
the
mixture was heated to ¨40 C and allowed to compatibilize. Once clear, the
mixture
was degassed, and cast into a 6" x 6"x 0.25" (15 cm x 15 cm x 0.6 cm) casting
cell
and aluminum cups preheated to 80 C. The filled cell was cured for 24 hours at
121 C.
1007511 An article of
6" x 6" x 1" thickness (15 cm x 15 cm x 2.5 cm) prepared
from this polymer stopped a 9 mm, 125 grain, bullet shot an initial velocity
of 1350
ft/sec (411 m/sec) from 20 feet (6.1 m) distance with little surface damage.
The
same sample also withstood a 0.40 caliber shot with little surface damage. The
bullets did not ricochet or embed in the polymer. The bullets were laying
partly
deformed at the bottom of the sample.
Example M3
[00752] A polyurethane
polymer according to the present invention was
prepared from the above isocyanate functional prepolymer,
cyclohexanedimethanol
(CHDM) and 1,4-butanediol as listed below:
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CA 02647153 2012-12-19
Desired
Polymer Batch
Solids Wt. (g) Size (g)
1,4-
Monomer Name Prepolymer CHDM butanediol 424.30 200.00
OH #
Acid #
Equivalent Wt. 365.71 72.11 45.06
Equivalents
desired 1.00 0.50 0.50
Mass Monomer 365.71 36.06 22.53
Weight %
Monomer 86.19% 8.50% 5.31%
Monomer
masses for
experiment 172.38 17.00 10.62
[00753] The prepolymer, CHDM (preheated to 80 C) and 1,4-
butanediol were added to a glass kettle. Under nitrogen blanket and with
constant
stirring, the mixture was heated to ¨40 C and allowed to compatibilize. Once
clear,
the mixture was degassed, and cast into a 6" x 6"x 0.25" (15 cm x 15 cm x 0.6
cm)
casting cell and aluminum cups preheated to 80 C. The filled cell was cured
for 24
hours at 121 C.
Example M4
[00754] A polyurethane polymer according to the present invention was
prepared from the above isocyanate functional prepolymer and hydroquinone
bis(hydroxyethyl) ether as listed below:
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Polymer Desired Batch
Solids Wt. (g) Size (g)
Hydroquinone
bis(hydroxyethyl) ether
Monomer Name Prepolymer 483.40 250.00
OH #
Acid #
Equivalent Wt. 384.29 99.11
Equivalents desired 1.00 1.00
Mass Monomer 384.29 99.11
Weight % Monomer 79.50% 20.50%
Monomer masses for
experiment 198.74 51.26
[00755] The prepolymer
and hydroquinone bis(hydroxyethyl) ether
were added to a glass kettle and placed in a heating mantle. Under nitrogen
blanket
and with constant stirring, the mixture was heated to ¨85 C and allowed to
compatibilize. Once clear, the mixture was placed under vacuum and degassed,
and
cast into a 6" x 6"x 0.25" (15 cm x 15 cm x 0.6 cm) casting cell preheated to
80 C.
The filled cell was cured for 24 hours at 121 C. The cast sample was clear,
but
showed some haze. The Gardner Impact Strength was 320 in-lbs (37 J).
Example N
[00756] An isocyanate
functional prepolymer was prepared by reacting the
following components:
Equivalent. Wt. Number of
Component Weight % equivalents
DESMODUR1 m W
4,4'-methylene-bis-(cyclohexyl 54.42
isocyanate) 131.2 0.42
DBT FASTCAT 4202
0.005
(dibutyl tin dilaurate)
PLURACOL'm E400NF
.095
(polyethylene glycol) 200 0.03
PLURONIC'm L62D
(ethylene oxide/propylene oxide 33.97
block copolymer) 1180 0.03
TRIMETHYLOPROPANE 2.32 45 0.05 ,
CAPATM 2077A
1.23
polycaprolactone polyol 375 0.003
Total 100.000000
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at a temperature of about 104 C for about 5 hours. All of the components were
mixed together, except the stabilizers which were dissolved after the
prepolymer was
reacted.
[00757] A polyurethane polymer according to the present invention was
prepared from the above prepolymer and 1,4-butanediol as listed below:
Polymer Desired Batch
Solids Wt. (g) Size (g)
Monomer Name Prepolymer 1,4-butanediol 375.38 100.00
OH #
Acid #
Equivalent Wt. 330.32 45.06
Equivalents
desired 1.00 1.00
Mass Monomer 330.32 45.06
Weight % Monomer 88.00% 12.00%
Monomer masses
for experiment 88.00 12.00
[00758] The prepolymer and 1,4-butanediol were added to a glass kettle.
Under nitrogen blanket and with constant stirring, the mixture was heated to
¨45 C
and allowed to compatibilize. Once clear, the mixture was degassed, and cast
into a
4" x 4"x 60 mil casting cell preheated to 80 C. The filled cell was cured for
24 hours
at 121 C.
[00759] An article of 6" x 6" x 1" (15 cm x 15 cm x 2.5 cm) prepared from
this
polymer stopped a 9 mm, 125 grain, bullet shot an initial velocity of 1350
ft/sec (411
m/sec) from 20 feet (6.1 m) distance with little surface damage. The same
sample
also withstood a 0.40 caliber shot with little surface damage.
Examples 0
Example 01
[00760] An isocyanate functional prepolymer was prepared by reacting the
following components:
213
Prepolymer Formulation
Equivalent Weight Normalized
Normalized Wt.
Component weight , Equivalents Wt. (g) % Equivalents to Des W
(g)
CAPA1m 2047 200.0 0.14 27.8 27.8% 0.28 56.68
CAPA1m 2077 375.0 0.018 6.65 ,6.7% 0.036
13.56
TMP 44.6 0.027 1.2 , 1.2% 0.055
2.45
OH Totals = - 0.18 35.65 - 0.37 72.69
0
Des W 131.2 0.49 64.35 64.4% 1.0000 131.20
0
Total = 78.5%
Prepolymer My, = 203.89 "
0,
0.
Prepolymer W
¨urethane = 28.94%
..3
1-,
Prepolymer Mc = 11150
01
w
Prepolymer Wb = 7433
1.)
0
1-,
1.)
1
1-,
1.)
1
1-,
ko
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CA 02647153 2012-12-19
at a temperature of about 104 C for about 5 hours. All of the components were
mixed together, except the stabilizers which were dissolved after the
prepolymer was
reacted.
[00761] A polyurethane
polymer according to the present invention was
prepared from the above prepolymer and CHDM as listed below:
Desired
Batch
Polymer Size
Solids Wt. (g) (g)
Monomer Name Prepolymer CHDM 402.98 800.00
OH #
Acid #
Equivalent Wt. 330.87 72.11
Equivalents
desired 1.00 1.0000
Mass Monomer 330.87 72.11
Weight %
Monomer 82.11% 9.01%
Monomer masses
for experiment 656.85 143.15
[00762] The prepolymer
and CHDM were added to a glass kettle. Under
nitrogen blanket and with constant stirring, the mixture was heated to ¨55 C
and
allowed to compatibilize. Once clear, the mixture was degassed, and cast into
a 13"
x 13"x 0.25" casting cell preheated to 80 C. The filled cell was cured for 24
hours at
121 C.
Example 02
[00763] A polyurethane
polymer according to the present invention was
prepared from the above prepolymer and CHDM as listed below:
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CA 02 647153 2012-12-19
Polymer Desired Batch
Solids Wt. (g) Size (g)
Monomer Name Prepolymer 2,2-thiodiethanol 391.97
700.00
OH #
Acid #
Equivalent Wt. 330.87 61.10
Equivalents desired 1.00 1.0000
Mass Monomer 330.87 61.10
Weight % Monomer 84.41% 15.59%
Monomer masses for
experiment 590.89 109.11
[00764] The prepolymer
and 2,2-thiodiethanol were added to a glass
kettle. Under nitrogen blanket and with constant stirring, the mixture was
heated to
¨55 C and allowed to compatibilize. Once clear, the mixture was degassed, and
cast into a 13" x 13"x 0.25" casting cell preheated to 80 C. The filled cell
was cured
for 24 hours at 121 C.
Example P
[00765] As a
comparative example, a thermoplastic polymer was
prepared using 1.0 equivalent of 1,10-decanediol and 1.0 equivalent of
DesmodurTM
W as reactants and 10 ppm dibutyltindiacetate as catalyst. The polymer was
mixed
at 110 C in a glass kettle under vacuum. After about 30 minutes at 110 C, the
mixture was cast between release coated glass molds and cured for 72 hours at
290 F (143 C). The mold was removed from the oven and the plastic released.
The
Gardner Impact strength was less than 40 in-lbs (5 J) and averaged about 16 in-
lbs
(2J).
[00766] A polymer
according to the present invention was prepared in a similar
manner using a small amount of a branched polyol, namely 0.05 equivalents of
trimethylolpropane, as well as 0.95 equivalents of 1,10-decanediol, and 1.0
equivalents of DesmodurTM W. The Gardner impact strength averaged 640-in-lbs
for
this branched thermoplastic with a molecular weight per crosslink of about
12,900
g rams/mole.
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Example Q
Comparative Example
[00767] For comparison,
a prepolymer was prepared by reacting about 0.1
equivalents of trimethylol propane with about 1.0 equivalent of 4,4'-methylene-
bis-
(cyclohexyl isocyanate) (DESMODURTm VV) to form a polyurethane polyisocyanate
dissolved in an excess (0.9eqs.) of DESMODURTm W. About 1Oppm of
dibutyltindiacetate was used as a catalyst. While mixing rapidly at room
temperature,
about 0.1 equivalents of 4,4'-methylene-bis-cyclohexylamine, a diamine analog
of
DESMODURTm W, was added. Immediately, a white, flaky precipitate formed. The
precipitate increased in concentration sitting overnight and would not
dissolve upon
heating up to about 290 F (143 C). The above example was repeated in the same
order as above, but the polyisocyanate was heated to about 40 C. While mixing
rapidly, the diamine was added and a similar white precipitate formed which
could
not be dissolved upon heating up to about 290 F (143 C).
[00768] According to
the present invention, the same polyisocyanate above
was heated to about 40 C. About 0.1 equivalents of water was added while
mixing
rapidly. Vacuum was applied (4mm Hg) to remove the carbon dioxide and a
polyurea formed within the polyurethane to form a polyurethane polyurea
polyisocyanate that was slightly hazy. The diamine analog of DESMODURTm W was
formed in situ when the water was reacted. This mixture was then reacted with
0.8
equivalents of trimethylolpropane to form a high modulus plastic with high
optical
clarity. The light transmittance of a 1/8" thick (0.3 cm) sample was 91.8%
with less
than 0.1% haze. The glass transition temperature was 175 C.
[00769] According to
the present invention, the same polyisocyanate was
reacted with 0.2 equivalents of water at about 40 C and the carbon dioxide
removed
via vacuum. The diamine analog of DESMODURTm W was formed in situ when the
water was reacted. About 0.5 equivalents of pentanediol and about 0.2
equivalents
of trimethylolpropane were reacted with the polyurethane polyurea
polyisocyanate to
form a high clarity optical plastic with a light transmittance of 91.74% for a
1/8" thick
(0.3 cm) sample and a glass transition temperature of about 137 C.
217
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Examples R
Example R1
[00770] In a glass kettle under nitrogen blanket with stirring, were
charged
8.26 weight% 3,6-dithia-1,2-octanediol (91.6 equivalent wt.); 29.47 weight%
bis(4-(-
hydroxyethoxy)-3,5-dibromophenyl) sulfone (326.985 equivalent wt.); 6.50
weight%
1,4-cyclohexanedimethanol (CHDM) (72.1 equivalent wt.); 5.10 weight%
trimethylolpropane (TMP) (44 equivalent wt.); 50.68 weight% 4,4'-methylenebis
(cyclohexyl isocyanate) (DESMODURTNA W) (131.2 equivalent wt.) preheated to a
temperature of 80 C. The mixture was heated to a temperature of 115 C.
[00771] The mixture was then degassed and cast into a 12"x13"x0.125" (30
cm x 33 cm x 0.3 cm) casting cell which had been preheated to a temperature of
121 C. The filled cell was then cured in an oven for a period of 48 hours at
121 C.
[00772] The refractive index of the resulting lens was measured as
np=1.5519.
Example R2
[00773] In a glass kettle under nitrogen blanket with stirring, were
charged
30.75 weight% 3,6-dithia-1,2-octanediol (91.6 equivalent wt.); 6.23 weight%
TMP
(44.0 equivalent wt.) and 62.92 weight% DESMODURTm W (131.2 equivalent wt.)
which was preheated to a temperature of 80 C. The mixture was heated to a
temperature of 105 C.
[00774] The mixture was then degassed and cast into a 12"x13"x0.125" (30
cm x 33 cm x 0.3 cm)casting cell which had been preheated to a temperature of
121 C. The filled cell was then cured in an oven fora period of 48 hours at
121 C.
[00775] The refractive index of the resulting lens was measured as
np=1.5448
and the impact as 82.0 in-lbs (9 J).
Example R3
[00776] In a glass kettle under nitrogen blanket with stirring, were
charged
9.70 weight% 1,5-pentanediol (52.1 equivalent wt.); 7.03 weight% TMP (44.0
equivalent wt.); 13.43 weight% CHDM (72.1 equivalent wt.) and 69.84%
DESMODURTm W (131.2 equivalent wt.) which was preheated to a temperature of
80 C. The mixture was heated to a temperature of 105 C.
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[00777] The mixture was then degassed and cast into a 12"x13"x0.125" (30
cm x 33 cm x 0.3 cm)casting cell which had been preheated to a temperature of
121 C. The filled cell was then cured in an oven for a period of 48 hours at
121 C.
[00778] The impact was measured as 160.0 in-lbs (18 J).
Example R4
[00779] This example was conducted in accordance with the procedure in
Example 3 with the exception that 1,4-butaned101 (45.1 equivalent wt.) was
used
instead of 1,5 pentanediol and CHDM was not present in the mixture. 17.28% 1,4
butanediol, 7.23% trimethylolpropane, and 75.48% DESMODURTm W.
[00780] The impact was measured as 120.0 in-lbs (14 J).
Example R5
[00781] This example was conducted in accordance with the procedure in
Example 4 with the exception that 1,4-benzenedimethanol (69.1 equivalent wt.)
was
used instead of 1,4-butanediol. 25.09 weight% 1,4 benzenedimethano1,6.85
weight%
trimethylolpropane, and 74.57 weight% DESMODURTm W.
[00782] The impact was measured as 72.0 in-lbs (8 J). It was observed that
after fifteen minutes into the cure cycle, the material turned hazy. Thus, the
oven
temperature had been increased to 143 C for the remainder of the cure cycle,
but the
material remained hazy.
Example R6
[00783] This example was conducted in accordance with the procedure in
Example 5 with the exceptions that 1,4-butanediol (45.1 equivalent weight) was
also
added to the mixture and the mixture was heated to a temperature of 115 C
instead
of 105 C. 13.12 weight% 1,4 benzenedimethanol, 8.55 weight% 1,4 butanediol,
and
71.17 weight% DESMODURTm W
[00784] The impact was measured as 72.0 in-lbs (8 J).
Example R7
[00785] This example was conducted in accordance with the procedure in
Example 6 with the exception that 1,6-hexanediol (59.1 equivalent wt.) was
used
instead of 1,4-butanediol. 12.76 weight% 1,4 benzenedimethanol, 10.93 weight%
1,6
hexanediol, and 69.32 weight% DESMODURTm W.
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CA 02647153 2012-12-19
[00786] The impact was measured as 64.0 in-lbs (7 J).
Example R8
[00787] This example was conducted in accordance with the procedure in
Example 7 with the exceptions that thiodiethanol (61.1 equivalent wt.) was
used
instead of 1,4-benzenedimethanol and the mixture was heated to a temperature
of
105 C instead of 115 C. 11.78 weight% 2,2-thiodiethanol, 8.69 weight% 1,4
butanediol, 7.27 weight% trimethylolpropane, and 70.10 weight% DESMODURTm W.
[00788] The impact was measured as 72.0 in-lbs (8 J).
Example R9
[00789] This example was conducted in accordance with the procedure in
Example 3 with the exceptions that CHDM was not present in the mixture and the
mixture was heated to a temperature of 115 C instead of 105 C. 20.16 weight%
1,5
pentanediol, 7.3 weight% trimethylolpropane, and 72.55 weight% DESMODURTm W.
[00790] The impact was measured as 200.0 in-lbs (23 J).
Example R10
[00791] This example was conducted in accordance with the procedure in
Example 9 with the exception that 1,8-octanediol (73.1 equivalent wt.) was
used
instead of 1,5-pentanediol. 26.14 weight% 1,8 octanediol, 6.75 weight%
trimethylol
propane, and 67.11 weight% DESMODURTm W.
[00792] The impact was measured as 624.0 in-lbs (72 J).
Example R11
[00793] This example was conducted in accordance with the procedure in
Example 10 with the exception that 1,10-decanediol (87.1 equivalent wt.) was
used
instead of 1,8-octanediol. 29.66 weight% 1,10 decanediol, 6.43 weight%
trimethylolpropane, and 63.9 weight% DESMODURTm W.
[00794] The impact was measured as 624.0 in-lbs (72 J).
Example R12
[00795] This example was conducted in accordance with the procedure in
Example 11 with the exceptions that ethyleneglycol (31.0 equivalent wt.) was
used
instead of 1,10-decanediol and the mixture was heated to a temperature of 105
C
220
CA 02647153 2012-12-19
instead of 115 C. 13.06 weight% ethylene glycol, 7.95 weight%
trimethylolpropane,
and 78.99 weight% DESMODURTm W
[00796] The impact was measured as 8.0 in-lbs (1 J).
Example R13
[00797] This example was conducted in accordance with the procedure in
Example 11 with the exception that 1,12-dodecanediol was used instead of 1,10-
decanediol. 32.87 weight% 1,12 dodecanediol, 6.14 weight% trimethylolpropane,
and
60.99 weight% DESMODURTm W.
[00798] The impact was measured as 624.0 in-lbs (72 J).
Example R14
[00799] This example was conducted in accordance with the procedure in
Example 13 with the exceptions that 1,6-hexanediol (59.1 equivalent wt.) was
used
instead of 1,12-dodecanediol and the mixture was heated to a temperature of
105 C
instead of 115 C. 22.24 weight% 1,6 hexanediol, 7.11 weight%
trimethylolpropane,
and 70.65 weight% DESMODURTm W.
[00800] The impact was measured as 144 in-lbs (17 J).
Example R15
[00801] This example was conducted in accordance with the procedure in
Example 9. The impact was measured as 80.0 in-lbs (9 J).
Example R16
[00802] This example was conducted in accordance with the procedure in
Example 11 with the exceptions that 101.2 equivalent wt of 1,10-decanediol was
used; and KM-1733 (a 1000 MW carbonate diol made from hexanediol and
diethylcarbonate, and commercially available from ICI) (428 equivalent wt.)
was
added to the mixture. 28.29% 1,10 decanediol, 9.48 weight% PC-1733, 5.69
weight%
trimethylolpropane, and 56.54 weight% DESMODURTNA W.
[00803] The impact was measured as 640.0 in-lbs (74 J).
Example R17
[00804] Formulations 1 through 11 were prepared in accordance with the
procedure of Example 3 with the exception that the components listed in Table
21
221
CA 02647153 2012-12-19
were used to prepare the reaction mixture. The resultant properties (including
tensile
strength at yield, % elongation at yield, tensile strength at break, %
elongation at
break, and Young's Modulus were measured in accordance with ASTM-D 638-03;
Gardner Impact was measured in accordance with ASTM-D 5420-04; Tg was
measured using Dynamic Mechanical Analysis; and Density was measured in
accordance with ASTM-D 792) of formulations 1 through 11 are shown in Tables
27-
29.
222
Table 27
Formulation # Component Equivalent Wt. Equivalents
Weight Weight % Wu (%) Wc( %) Mc (g/mole)
(glEq.) _
1 TMP 44.7 0.3 13.40 6.5
28.7 39.4 2055
. _
1,10 dodecanediol 87.1 0.7 _ 60.97 29.7
DESMODUR1 M W 131.0 1.0 131.0 63.8
_
2 TMP 44.7 0.3 13.40 6.7
29.4 40.4 2006
1,10 dodecanediol 87.1 0.35 30.48 15.2
1,8 octanediol 73.1 0.35 25.58 12.7
, DESMODUR-im W 131.0 1.0 131.0 65.4
o
_
o
3 TMP 44.7 0.3 13.40 7.61
33.5 46.04 1759 n.)
cn
1,4 butanediol 45.0 0.7 , 31.5
17.9 .o.
-.3
DESMODURI m W 131.0 1.0 131.0 74.49
(xi
w
4 TMP 44.7 0.3 13.40 7.40
32.6 44.8 1808 n.)
_
o
1,5 pentanediol 52.0 0.7 36.4 20.13
n.)
DESMODURTm W 131.0 1.0 131.0 72.47
1
1-,
n.),
1
TMP 44.7 0.6 26.82 11.64 33.0 45.81 1786
1,5 pentanediol 52.0 0.4 20.8 15.06
ko
DESMODURTm W 131.0 1.0 131.0 73.3
6 TMP 44.7 0.3 13.40 7.20 31.77 43.62
1857
1,6 hexanediol 59.0 0.7 41.3 22.26
DESMODUFem W 131.0 1.0 131.0 70.54
7 TMP 44.7 0.3 13.40 6.81
30.44 1938
1,4 CHDM 72.11 0.35 25.24 13.02
1,6 BDM 69.08 0.35 24.18 12.48
DESMODUR1 m W 131.0 1.0 131.0 131.0
223
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Table 28
Formulatio Component Equivalen Equivalent Weigh Weigh Wu Wc Mc
n # t Wt. s t t % (%) (%) (g/mole
(g/Eq.)
8 TMP 44.7 0.3 13.40 7.03 31.4 43.1 1879
1
1,4 CHDM 72.11 0.35 25.24 13.43
1,5 52.0 0.35 18.23 9.70
pentanediol
9 TMP 44.7 0.3 13.40 6.94 31.0 42.5 1903
1,4 CHDM 72.11 0.35 25.24 13.26
1,6 hexanediol 59.09 0.35 20.68 10.87
DESMODURT 131.0 1.0 131.0 68.94
W
TMP 44.7 0.3 13.20 6.7 30.2 41.4 1956
1,8 octanediol 73.1 0.7 51.17 26.2
DESMODURT 131.0 1.0 1.0 67.1
MW
11 TMP 44.7 0.3 13.40 6.33 28.2 38.8 2085
9 4
3,6-dithia-1,2
octanediol 91.6 0.7 64.12 30.75
DESMODURT 131.0 1.0 131.0 62.92
rvi
Note: Formula 11 has a refractive index of 1.55 and a Gardner Impact strength
of 65 in-lbs.
224
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Table 29
Formula Tensile yo Tensile oh Young's Gardner Tg Density
Strength Elongation Strength Elongation Modulus Impact gicc
At Yield At Yield At Break At Break (Psi) In-lbs
(Psi) (Psi) (Psi) (Psi)
1 9190 7.4 6710 57 268,000 600 99.1 1.091
2 9530 7.5 7030 65 282,000 592 102 1.093
3 12,100 9.2 9040 41 336,000 120 126 1.14
4 11,200 8.7 8230 38 321,000 190 119 1.13
13,100 9.6 11,000 19 351,000 71 140 1.13
6 11,000 8.7 8300 56 311,000 130 117 1.12
7 13,600 10 12,100 18 360,000 75 156 1.13
8 12,100 9.8 9380 32 339,000 143 132 1.12
9 11,900 9.4 8880 34 327,000 124 130 1.14
9880 7.9 7480 55 287,000 600 106 1.10
11 - - - - - 65 - -
225
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Example R18
[00805] This example was conducted in accordance with the procedure in
Example 12 with the exceptions that 53.0 equivalent wt. of diethylene glycol
was
used instead of ethylene glycol and the mixture was heated to a temperature of
115 C instead of 105 C.
[00806] The impact was measured as 6.0 in-lbs.
Example R19
[00807] This example was conducted in accordance with the procedure in
Example 18 with the exception that 67.0 equivalent wt. dipropylene glycol was
used
instead of diethylene glycol.
[00808] The impact was measured as 8.0 in-lbs.
[00809] After curing, a set of the sheets coated with each of the polymers
A-D
were abrasion tested using a standard Taber abrasion test with CS1OF wheels
(one
pair for all samples), 500 grams each wheel. The wheels were re-surfaced
before
each cycle (25 cycles). Test conditions were conducted at a temperature of
ranging
from about 70 F to about 75 F and about 50% to about 60 % relative humidity.
Average scattered light haze for a given number of Taber cycles was
determined,
with the results shown below.
1008101 Standard QUV-B exposure test procedure over a period of 1000
hours, representing the equivalent of about three years of outdoor exposure.
The
results are shown below.
Exposed Samples ¨ 1000 hours QUV-B Exposure ¨ 3 yr. Equivalent Outdoor
Coated with A) Haze at number of
Cycles
Sample 0 100 300 500 1000
Polymer A
Polymer B
Polymer C
Polymer D
226
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Example S: Fire Retardance Testing
Example Si
1008111 A polyurethane polymer according to the present invention was
prepared from the components listed below:
Desired
Polymer Batch
Solids Wt. (g) Size (g)
Tetrabromobisphenol
Monomer A bis(2-hydroxyethyl) 1,6-
Name ether hexanediol TMP Des W 291.54 100.00
OH #
Acid #
Equivalent
Wt. 315.99 59.09 44.00 131.2
Equivalents
desired 0.4000 0.5000 0.100 :1.000
Mass
Monomer 126.40 29.55 4.40 131.20
Weight %
Monomer 43.35% 10.13% 1.51% 45.00%
Monomer
masses for
experiment 43.35 10.13 1.51 45.00
Weight %
Urethane 20.24
Molecular
Weight per
Crosslink
(g/mole)
(Mc 8746.23
[00812] The 1,6-hexanediol, trimethylolpropane and DESMODURTm W
preheated to 80 C were added to a glass beaker along with solid
tetrabromobisphenol A bis(2-hydroxyethyl) ether. While stirring on a hotplate,
the
mixture was heated until the mixture had cleared and all solid
tetrabromobisphenol A
bis(2-hydroxyethyl) ether had dissolved / melted.
[00813] Initial Gardner impact data showed better impact strength than
stretched acrylic (>16 in/lbs), and much higher than PLEXIGLASTM (2 in-lb).
Burn
testing with a Bunsen burner showed that the flame was immediately self-
extinguishing.
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Example S2
1008141 A polyurethane polymer according to the present invention was
prepared from the components listed below:
Desired
Batch
Solids Size (g)
Tetrabromobisphenol
A
bis(2-hydroxyethyl) 1,6-
Monomer Name ether hexanediol TMP Des W 475.00
OH #
Acid #
Equivalent Wt. 315.99 59.09 44.00 131.2
Equivalents
desired 0.4500 0.4500 0.100 1.000
Mass Monomer 142.20 26.59 4.40 131.20
Weight %
Monomer 46.72% 8.74% 1.45% 43.10%
Monomer
masses for
experiment 221.90 41.49 6.87 204.74
Weight %
Urethane 19.38
Molecular
Weight per
Crosslink
(g/mole) (Mc 9131.58
1008151 The polymer weight was 304.39 grams. The 1,6-
hexanediol,
trimethylolpropane and DESMODURTm W preheated to 80 C were added to a glass
kettle along with solid tetrabromobisphenol A bis(2-hydroxyethyl) ether. Under
nitrogen blanket and with constant stirring, the mixture was heated to ¨105 C,
until
the mixture had cleared and all solid tetrabromobisphenol A bis(2-
hydroxyethyl) ether
had dissolved / melted. Once clear, the mixture was degassed, and cast into a
12"x12"x0.125" casting cell preheated to 121 C. The filled cell is cured for
48 hours
at 121 C. Initial impact data showed very poor performance (<16 in / lbs).
Burn
testing with a Bunsen burner showed that the flame was immediately self-
extinguishing.
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Example S3
1008161 A polyurethane polymer according to the present invention was
prepared from the components listed below:
Desired
Batch
Solids Size (g)
Tetrabromobisphenol
Monomer A bis(2-hydroxyethyl) 1,6-
Name ether hexanediol TMP Des W 300.00
OH # - - - -
Acid # - - - -
Equivalent
Wt. 315.99 59.09 44.00 131.2
Equivalents
desired 0.1000 0.8000 0.100 1.000
Mass
Monomer 31.60 47.27 4.40 131.20
Weight %
Monomer 14.73% 22.04% 2.05% 61.17%
, _________________________________________________
Monomer
masses for
experiment 44.20 66.12 6.15 183.52
_
Weight %
Urethane 27.51
Molecular
Weight per
Cross link
(g/mole) (Mc 6434.13
[00817] The polymer weight was 214.47 grams. The 1,6-hexanediol,
trimethylolpropane and DESMODURTm W preheated to 80 C were added to a glass
kettle along with solid tetrabromobisphenol A bis(2-hydroxyethyl) ether. Under
nitrogen blanket and with constant stirring, the mixture was heated to ¨105 C,
until
the mixture had cleared and all solid tetrabromobisphenol A bis(2-
hydroxyethyl) ether
had dissolved / melted. Once clear, the mixture was degassed, and cast into a
12"x12"x0.125" casting cell preheated to 121 C. The filled cell is cured for
48 hours
at 121 C. Burn testing with a Bunsen burner showed that the polymer charred
and
burned for about 7 seconds after the flame was removed.
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Example T
Fiberglass Reinforced Polyurethane
1008181 The following reactants: 208 grams of 1,10-decanediol (2.39
equivalents) and 45.7 grams of trimethylolpropane (1.02 equivalents) were
charged
into a flask and heated to 125 C under a nitrogen blanket with stirring. When
a clear,
homogenous melt was formed the mixture was cooled to 105 C and 446 grams (3.41
equivalents) of DESMODURTm W were added. After mixing for 15 minutes and
reheating to about 90 C the mixture clarified. After controlling the
temperature at
90 C for about 10 minutes, approximately 50% of the liquid was vacuum
transferred
into a 20" by 20" by 1/8" (50.8 cm x 50.8 cm x 0.3 cm) thick mold containing 4
layers
of bidirectional E-glass fiber mat covered by release fabric and flow mesh
inside a
vacuum bag. The mold and glass were preheated to 105 C before beginning the
transfer.
1008191 After approximately 15 minutes sufficient material was transferred
to
completely fill the bag and wet the fiberglass. The bag and mold were then
heated to
143 C for 48 hours. The temperature of the resulting fiberglass-urethane
composite
was then reduced to 120 C and held for 1 hour, followed by a further reduction
in
temperature to 38 C. After a one hour hold at 38 C the system was cooled to
room
temperature and disassembled. The resulting part was rigid, colorless and void-
free.
Example U
Multilayer Composite of Cast Film According to the Present Invention on
Stretched
Acrylic
1008201 A casting cell was constructed using 0.5" Polycast 84 stretched
acrylic and 0.25" of glass that was release coated with
dimethyldichlorosilane. A
primer was applied to the stretched acrylic for good urethane adhesion. The
cell was
6" x 6" with a 0.060" gap between the glass and the stretched acrylic held
constant
with a silicone rubber gasket. The edges were clamped. A composition using 0.3
equivalents of trimethylolpropane, 0.7equivalents of 1,5 pentanediol, and 1.0
equivalents of DESMODURTm W were mixed and degassed at 210 F and poured into
the described casting cell. The composition was cured at 180 F for 3 days,
allowed
to cool to room temperature, and then the film-cast plastic was separated from
the
glass release plate. A high optical quality composite was produced that had
excellent substrate adhesion and high resistance to solvent stress-craze
resistance.
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The composite was stressed to 4,000 psi with the polyurethane plastic in
tensile
stress and ethyl acetate was applied, covered with a glass cover slip and
allowed to
sit for 30 minutes. No crazing was observed even under microscopic
examination.
The same test was done on bare stretched acrylic in which crazes are
immediately
visible without microscopic examination. The same test was run on bare
stretched
acrylic stressed to 1000 psi. Crazing was again immediately visible without
microscopic examination.
Examples V
Reinforced Composites
1008211 With reference to Table 30 below, a thermoset polyurethane was
prepared as follows:
100822] A reaction vessel was equipped with a stirrer, thermocouple,
nitrogen
inlet, distillation container and vacuum pump. Charge A was then added and
stirred
with heating to 80 C-100 C under vacuum and held for 1 hour. The reaction
mixture
was then cooled to 80 C, vacuum turned off and Charge B was added to the
vessel.
The reaction mixture was then heated to 80 C under vacuum and allowed to
exotherm from 110 C-120 C. The reaction mixture was then cast in place between
two 5 inch by 5 inch by three sixteenths inch float glass plates which were
fitted with
gaskets on three sides and held together using clamps. Both glass plates had a
silane release coating on their faces that contacted the polyurethane. The
spacing
between the plates was approximately three sixteenths of an inch. The casting
cell
was preheated to a temperature of about 120 C before casting. After casting,
the
assembly was given a 24 hour cure at 120 C and then a 16 hour cure at 143 C.
After curing was complete, the cell was given a two hour gradual cool down
cycle
from the 143 C temperature to 45 C while remaining in the oven. The cell was
removed from the oven and the glass plates were separated from the
polyurethane.
Table 30
Charge A Parts by Weight
1,10-Decanediol 61.00
Trimethylolpropane 13.41
_Charge B
DesmoduriM W1 131.00
1 Bis(4-isocyanatocyclohexyl)methane from Bayer Material Science.
231
CA 02647153 2012-12-19
Example V
[00823] The following Examples show the infusion of various inorganic
particulate phases into a thermoset polymeric phase. The thermoset polymers
were
contacted with various swelling solvents and various precursors that formed
the
inorganic particulate phase in situ.
Example V1
Infusion of tetramethyl orthosilicate in methanol
[00824] The thermoset polyurethane of Example A was immersed into a
solution comprising 20.3% by weight (25% by volume) of anhydrous methanol and
79.7% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for 24
hours.
The poly(urethane) was removed from the methanol/TMOS solution and placed into
deionized water for three days. The poly(urethane) was subsequently placed in
a
vacuum oven at 100 C for 2 hours. Transmission electron microscopy (TEM)
indicated that silica particles had infused into the polyurethane phase. The
silica
particles had generated 250 pm into the poly(urethane) substrate. Silica
nanoparticle
morphology was generally spherical and the particle size ranged from 10 to 20
nm.
Discrete particles and clusters of particles were seen in this specimen.
Example V2
Infusion of tetraethyl orthosilicate in ethanol
[00825] The thermoset polyurethane of Example A was immersed into a
solution comprising 21.9% by weight (25% by volume) of anhydrous ethanol and
78.1% by weight (75% by volume) of tetraethyl orthosilicate (TEOS) for 24
hours.
The poly(urethane) was removed from the ethanol/TEOS solution and placed into
a
14% aqueous solution of ammonium hydroxide for four hours. The poly(urethane)
was rinsed with water and placed into an oven at 143 C for four hours. TEM
indicated silica nanoparticles had infused into the polyurethane phase. The
nanoparticles ranged in size from 10 to70 nm with most being in the 10 nm
range.
Example V3
Infusion of tetramethyl orthosilicate in xvIene
[00826] The thermoset polyurethane of Example A was immersed into a
solution comprising 21.7% by weight (25% by volume) of anhydrous xylene and
78.3% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for 24
hours.
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The poly(urethane) was removed from the xylene/TMOS solution and placed into a
14% aqueous solution of ammonium hydroxide for four hours. The poly(urethane)
was rinsed with water and placed into an oven at 143 C for four hours. TEM
indicated silica nanoparticles had infused into the polyurethane phase. The
nanoparticles ranged in size from 7 to 40 nanometers.
Example V4
Infusion of tetramethyl orthosilicate in ethyl acetate
[00827] The thermoset
polyurethane of Example A was immersed into a
solution comprising 22.4% by weight (25% by volume) of anhydrous ethyl acetate
and 77.6% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for 24
hours. The poly(urethane) was removed from the ethyl acetate/TMOS solution and
placed into a 14% aqueous solution of ammonium hydroxide for four hours. The
poly(urethane) was rinsed with water and placed into an oven at 143 C for four
hours. TEM indicated silica nanoparticles had infused into the polyurethane
phase.
Example V5
Infusion of tetramethyl orthosilicate in dimethyl sulfoxide
[00828] The
polyurethane of Example A was immersed into a solution
comprising 25% by weight (25% by volume) of anhydrous dimethyl sulfoxide
(DMSO)
and 75% by weight (75% by volume) of tetramethyl orthosilicate (TMOS) for 24
hours. The poly(urethane) was removed from the DMSO/TMOS solution and placed
into a 14% aqueous solution of ammonium hydroxide for four hours. The
poly(urethane) was rinsed with water and placed into an oven at 143 C for four
hours. TEM indicated silica nanoparticles had infused into the polyurethane
phase.
The nanoparticles ranged in size from 7 to 30 nanometers.
Example V6
Infusion of tetramethyl orthosilicate into a crosslinked polyester film
[00829] A piece of
crosslinked polyester film was immersed into a solution
comprising 20.3% by weight (25% by volume) of anhydrous methanol and 79.7% by
weight (75% by volume) of tetramethyl orthosilicate (TMOS) for two hours. The
film
was removed from the methanol/TMOS solution and placed into a 14% aqueous
solution of ammonium hydroxide for two hours. The film was rinsed with water
for 15
minutes and allowed to dry at room temperature for 17 hours. A silica
particulate
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phase infused into the polymeric phase. TEM indicated the nanoparticles ranged
in
size from 7 to 300 nm.
Example V7
Infusion of titanium bis(ethyl acetoacetato) diisopropoxide in ethyl acetate
[00830] The thermoset polyurethane of Example A was immersed into a
solution comprising 80.1% by weight of anhydrous ethyl acetate and 19.9% by
weight
of titanium bis(ethyl acetoacetato) diisopropoxide for 24 hours. The
poly(urethane)
was removed from the ethyl acetate/titanium bis(ethyl acetoacetato)
diisopropoxide
solution and placed into a 14% aqueous solution of ammonium hydroxide for four
hours. The poly(urethane) was rinsed with water and placed into an oven at 143
C
for four hours. A titania particulate phase infused into the polyurethane
phase. Tern
indicated the nanoparticles ranged in size from 5 to 200 nm.
Example V8
Infusion of zirconium(IV) acetylacetonate in ethyl acetate
[00831] The thermoset polyurethane of Example A was immersed into a
solution comprising 91.2% by weight of anhydrous ethyl acetate and 8.8% by
weight
of zirconium(IV) acetylacetonate for 24 hours. The poly(urethane) was removed
from
the ethyl acetate/zirconium(IV) acetylacetonate solution and placed into a 14%
aqueous solution of ammonium hydroxide for four hours. The poly(urethane) was
rinsed with water and placed into an oven at 143 C for four hours. A zirconia
particulate phase infused into the polyurethane phase.
Examples W
Synthesis of Acrylic Silane Polymers
[00832] For each of Examples A to C in Table 23, a reaction flask was
equipped with a stirrer, thermocouple, nitrogen inlet and a condenser. Charge
A was
then added and stirred with heat to reflux temperature (75 C-80 C) under
nitrogen
atmosphere. To the refluxing ethanol, charge B and charge C were
simultaneously
added over three hours. The reaction mixture was held at reflux condition for
two
hours. Charge D was then added over a period of 30 minutes. The reaction
mixture
was held at reflux condition for two hours and subsequently cooled to 30 C.
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Table 31
Example A Example B Example C
Charge A (weight in grams)
Ethanol SDA 4061 360.1 752.8 1440.2
Charge B (weight in grams)
Methyl Methacrylate 12.8 41.8 137.9
Acrylic acid 8.7 18.1 34.6
Si!quest A-1742 101.4 211.9 405.4
2-hydroxylethylmethacrylate 14.5 0.3 0.64
n-Butyl acrylate 0.2 0.3 0.64
Acrylamide 7.2
Sartomer SR 3553 30.3
Ethanol SDA 40B 155.7 325.5 622.6
Charge C (weight in grams)
Vazo 674 6.1 12.8 24.5
Ethanol SDA 40B 76.7 160.4 306.8
Charge D (weight in grams)
Vazo 67 1.5 2.1 6.1
Ethanol SDA 40B 9.1 18.9 36.2
% Solids 17.9 19.5 19.1
Acid value (100% resin solids) 51.96 45.64 45.03
Mn 30215 5810
1 Denatured ethyl alcohol, 200 proof, available from Archer Daniel Midland Co.
2 gamma-methacryloxypropyltrimethoxysilane, available from GE silicones.
3 Di-trimethylolpropane tetraacrylate, available from Sartomer Company Inc.
2,2'-azo bis(2-methyl butyronitrile), available from E.I. duPont de Nemours &
Co.,
Inc.
Mn of soluble portion; the polymer is not completely soluble in
tetrahydrofuran.
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Example W1
[00833] The acrylic-silane resin from Example A (8.5 grams) was blended
with
polyvinylpyrrolidone (0.1 grams) and water (1.5 grams). The formulation was
stored
at room temperature for 225 minutes. A portion of the resulting solution was
loaded
into a 10 ml syringe and delivered via a syringe pump at a rate of 1.6
milliliters per
hour to the spinneret as described in Example 1. The conditions for
electrospinning
were as described in Example 1. Ribbon shaped nanofibers having a thickness of
100-200 nanometers and a width of 1200-5000 nanometers were collected on
grounded aluminum foil and were characterized by optical microscopy and
scanning
electron microscopy. A sample of the nanofiber was dried in an oven at 110 C
for
two hours. No measurable weight loss was observed. This indicates the
nanofibers
were completely crosslinked.
Examples W2 and W3
[00834] Transparent composite articles comprising a polyurethane matrix and
electrospun fibers of Example 1 were prepared as follows:
[00835] For each of Examples 2 and 3, see Table 32 below, a reaction vessel
was equipped with a stirrer, thermocouple, nitrogen inlet, distillation
container and
vacuum pump. Charge A was then added and stirred with heating to 80 C-100 C
under vacuum and held for 1 hour. The reaction mixture was then cooled to 80
C,
vacuum turned off and Charge B was added to the vessel. The reaction mixture
was
then heated to 80 C under vacuum and allowed to exotherm from 110 C-120 C. The
reaction mixture was then cast in place between two 5 inch by 5 inch by three
sixteenths inch float glass plates which were fitted with gaskets on three
sides and
held together using clamps. Both glass plates had a silane release coating on
their
faces that contacted the electrospun fibers and the polyurethane. The fibers
were
spun over the treated plates before assembling them into a casting cell. The
casting
cell was assembled with the electrospun nanofiber covered plate on the inside
of the
casting cell. The spacing between the plates was approximately three
sixteenths of
an inch. The casting cell was preheated to a temperature of about 120 C before
casting. After casting, the assemblies were given a 24 hour cure at 120 C and
then a
16 hour cure at 143 C. After curing was complete, the cells were given a two
hour
gradual cool down cycle from the 143 C temperature to 45 C while remaining in
the
oven. The cells were removed from the oven and the glass plates were separated
from the composite article.
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Polyurethane Examples 2 and 3
TABLE 32
Charge A (weight in grams) Example 2 Example 3
1, 4 Butanediol 31.54
1, 10 Decanediol 61.00
Trimethylolpropane 13.41 13.41
Charge B (weight in grams)
DesmodurT"W 131.00 131.00
Bis(4-isocyanatocyclohexyl)methane from Bayer Material Science.
1008361 Each composite article was tested for scratch resistance by
subjecting
the composite to scratch testing by linearly scratching the surface with a
weighted
abrasive paper for ten double rubs using an Atlas ATCC Scratch Tester, Model
CM-
5, available from Atlas Electrical Devices Company of Chicago, Illinois. The
abrasive
paper used was 3M 281Q WETORDRYTm PRODUCTIONTm 9 micron polishing paper
sheets, which are commercially available from 3M Company of St. Paul,
Minnesota.
1008371 After completing the scratch-test with a Crockmeter using a 9-pm
abrasive, the increase in the average roughness in the surface of the
scratched area
was measured using an optical profilometer. The surface of the scratched area
was
scanned perpendicular to the direction on the Crockmeter scratching; that is,
across
the scratches. An identical scan was taken in an unscratched area to measure
average roughness of the surface of the original article. Change in average
surface
roughness for each article was calculated by subtracting the average roughness
of
the unscratched surface from the average roughness of the scratched surface.
Transparent articles with no nanofibers were compared with transparent
composite
articles containing electrospun fibers from Example 3.
[008381 Also, for the purpose of comparison, composite articles were
prepared
as generally described above for Example 3 but in which polyvinylidene
fluoride
(KYNARTM) and nylon-6 fibers were electrospun and used in place of the fibers
of
Example 3. The composite articles were evaluated for scratch resistance as
described above. The results of the testing are reported in Table 33 below.
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CA 02647153 2012-12-19
Table 33
Change in average
Example Electrospun Fibers surface roughness
(nm)
Control None 74.54
Example 4 Example 3 6.93
Example 4 (repeat) Example 3 -7.28
Control (repeat) None 81.48
Example 5 Example 3 -4.91
Comparative KYNARTM 90.2
Comparative Nylon-6 66.96
[00839] The results reported in Table 33 show the improvement in scratch
resistance provided by the acrylic-silane electrospun fibers.
Example X
Powder Example
[00840] 1,4-Butanediol (5.47 grams, 0.122 equivalents) and 4,4'-methylene
bis-cyclohexylisocyanate (DESMODURTm W from Bayer Corporation; NCO
equivalent weight 131; 14.52 grams, 0.111 equivalents) were stirred together
in a dry
glass container. One drop of dibutyltin dilaurate was added. The cloudy
mixture
warmed spontaneously and became transparent. The mixture was then placed in an
oven at 120 C for 6 hours.
[00841] A 1.88 gram portion of the resulting glassy, solid polyurethane was
dissolved in 5.23 grams of M-Pyrol by boiling on a hot plate. Similarly,
isophorone
diisocyanate trimer (0.23 grams) was dissolved in 3.68 grams of M-Pyrol. The
two
solutions were combined in an aluminum dish and baked at 145 C for 35 minutes.
The resulting film was transparent, tough and hard. Rubbing with methyl ethyl
ketone did not soften the film or cause it to become tacky, indicating it was
thoroughly crosslinked.
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Example Y
Liquid Infusion of Inorganic Precursors into Urethane Resulting in In-Situ
Generated
Nanoparticles
[00842] A piece of urethane plastic was prepared by the following method.
Dimethyl dichlorosilane was vapor deposited onto the surface of two pieces of
tempered glass and the excess was wiped off with isopropanol. A rubber gasket
(3/16" in diameter) was placed between the two pieces of glass and the pieces
of
glass were fastened together so that one end of the mold was open. The pre
polymer
was prepared by heating 504 g 1,10-decanediol (3.55 mol, 0.7 equivalents) and
111
g trimethylolpropane (0.83 mol, 0.3 equivalents) in a three-neck round bottom
flask to
120 C under vacuum, where it was held for 30 minutes. The contents of the
flask
were cooled to 80 C and 1084 g dicyclohexylmethane diisocyanate (4.14 mol, 1
equivalent) was added. The reaction exothermed to 105 C and the solution was
poured into the open end of the glass mold. The mold was placed into an oven
at
120 C for 24 hours and 143 C for 16 hours. The temperature was decreased to
43 C for one hour and the mold was removed from the oven. The mold was
disassembled to remove the cast urethane plastic part.
[00843] A solution comprising 75% by volume of tetramethylorthosilicate
(TMOS) and 25% by volume of methanol was prepared in a sealed container. A
piece of urethane plastic was placed into the sealed container and the
container was
flushed with dry nitrogen gas. The urethane plastic soaked in the
TMOS/methanol
solution for 4 or 24 hours. The urethane plastic was removed and immersed in:
1)
water for 72 hours, 2) 2 M HCI for one hour and water for one hour or 3) 15%
v/v
solution of NH4OH in water for one hour and water for one hour. The specimens
were subsequently annealed at 143 C for 4 hours. The immersion soaks
hydrolyzed
and condensed the liquid inorganic precursor (TMOS) that was infused in the
plastic.
Each soak resulted in different sized nanoparticles which were located at
different
depths in the plastic.
It will be appreciated by those skilled in the art that changes could be made
to the
embodiments described above without departing from the broad inventive concept
thereof. It is understood, therefore, that this invention is not limited to
the particular
embodiments disclosed, but it is intended to cover modifications which are
within the
scope of claims.
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